Avermectin and avermectin monosaccharide derivatives substituted in the 4″-or 4′-position having pesticidal properties

ABSTRACT

What is described are a compound of the formula (I) Wherein U is —N(R 2 )OR 3  or —N + (O − )═C(R E )R Z ); n is 0 or 1; X—Y is —CH═CH— or —CH 2 —CH 2 —; R 1  is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl or C 2 -C 12 alkenyl; R 2  and R 3  are, for example; independently from each other, —Q, —C(═O)—Z—Q or —CN; R Z  and R E  are, independently from each other, —Q, —C(═O)—Z—Q or —CN; or R Z  and R E  together are a three- to seven membered alkylene or alkenylene bridge, which is unsubstituted or mono- to tri-substituted; Z is a bond, O or —NR 4 —; Q is H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 3 -C 12 -Cycloalkyl, C 5 -C 12 -cycloalkenyl, aryl, or heterocyclyl, which are unsubstituted or mono- to pentasubstituted; R 4  is for example H, C 1 -C 8 alkyl, hydroxy-C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl or C 2 -C 8 alkenyl; or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomer thereof; a process for preparing these compounds, their isomers and tautomers and the use of these compounds, their isomers and tautomers; pesticidal compositions whose active compound is selected from these compounds and their tautomers; intermediates for the preparation of the said compounds of the formula (I), methods for the preparation of the compounds of the formula (I), and a method for controlling pests using these compositions.

This application is a 371 of International Application No.PCT/EP2004/000890 filed Jan. 30, 2004, which claims priority to GB0302308.2, filed Jan. 31, 2003, the contents of which are incorporatedherein by reference.

The invention relates (1) to compound of the formula

wherein

U is —N(R₂)OR₃ or —N⁺(O⁻)═C(R_(E))R_(Z));

n is 0 or 1;

X—Y is —CH═CH— or —CH₂—CH₂—;

R₁ is C₁-C₁₂alkyl, C₃-C₈cycloalkyl or C₂-C₁₂alkenyl;

R₂ and R₃ are, independently from each other, —Q, —C(═O)—Z—Q or —CN; or

R₂ and R₃ together are a three- to seven membered alkylene or alkenylenebridge, which is unsubstituted or mono to tri-substituted;

R_(Z) and R_(E) are, independently from each other, —Q, —C(═O)—Z—Q or—CN; or

R_(Z) and R_(E) together are a three- to seven membered alkylene oralkenylene bridge, which is unsubstituted or mono to tri-substituted;

Z is a bond, O or —NR₄—;

R₄ is H, C₁-C₈alkyl, hydroxy-C₁-C₈alkyl, C₃-C₈cycloalkyl, C₂-C₈alkenyl,C₂-C₈alkynyl, phenyl, benzyl —C(═O)R₅, or —CH₂—C(═O)—R₅;

Q is H, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂-cycloalkyl,C₅-C₁₂-cycloalkenyl, aryl, or heterocyclyl, which are unsubstituted ormono- to pentasubstituted;

wherein the alkyl-, alkenyl-, alkynyl-, alkylene-, alkenylene-,cycloalkyl-, cycloalkenyl-, aryl- and heterocyclyl-radicals of thesubstituents Q, R₂, R₃, R₄, R_(Z), R_(E) and Q are independently of eachother selected from the group consisting of OH, ═O, SH, ═S, halogen, CN,—N₃, SCN, NO₂, Si(C₁-C₈alkyl)₃, halo-C₁-C₂alkyl,C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy,C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl,C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy,C₂-C₁₂alkenylthio, C₂-C₁₂halo-alkenylthio, C₂-C₁₂alkenylsulfinyl,C₂-C₁₂haloalkenylsulfinyl, C₂-C₁₂alkenylsulfonyl,C₂-C₁₂haloalkenylsulfonyl, C₃-C₈cycloalkyl which is unsubstituted orsubstituted by one to three methyl groups, norbornylenyl,C₃-C₈halocycloalkyl, C₁-C₁₂alkoxy, C₃-C₈cycloalkoxy, C₁-C₁₂alkylthio,C₃-C₈cycloalkylthio, C₁-C₁₂haloalkylthio, C₁-C₁₂alkyl-sulfinyl,C₃-C₈cyclo-alkylsulfinyl, C₁-C₁₂haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₁-C₁₂alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₁₂haloalkylsulfonyl,C₃-C₈halocycloalkylsulfonyl, C₂-C₈alkenyl, C₂-C₈alkynyl, —N(R₈)₂ whereinthe two R₈ are independent of each other, —C(═O)R₅, —O—C(═O)R₆,—NHC(═O)R₅, —S—C(═S)R₆, —P(═O)(OC₁—C₆alkyl)₂, —S(═O)₂R₉; —NH—S(═O)₂R₉,OC(═O)—C₁-C₆alkyl-S(═O)₂R₉, aryl, benzyl, heterocyclyl, aryloxy,benzyloxy, heterocyclyloxy, arylthio, benzylthio, heterocyclylthio;wherein the aryl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy,arylthio, benzylthio and heterocyclylthio radicals are eitherunsubstituted or, depending on the possibilities of substitution on thering, mono- to pentasubstituted by substituents selected from the groupconsisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl,Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy,C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl,C₃-C₁₂haloalkynyloxy, C₃-C₈cycloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl,dimethylamino-C₁-C₆alkoxy, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy,phenyl-C₁-C₆alkyl, methylenedioxy, —C(═O)R₅, —O—C(═O)—R₆, —NH—C(═O)R₆,—N(R₈)₂, wherein the two R₈ are independent of each other,C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl andC₃-C₈halocycloalkylsulfonyl;

R₅ is H, OH, SH, —N(R₈)₂ wherein the two R₈ are independent of eachother, C₁-C₂₄alkyl, C₂-C₁₂alkenyl, C₁-C₈hydroxyalkyl, C₁-C₁₂haloalkyl,C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₁₂alkylthio, C₂-C₈alkenyloxy, C₃-C₈alkynyloxy, Si(C₁-C₈alkyl)₃,C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy,C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl,C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy,NH—C₁-C₆alkyl-C(═O)R₇, —N(C₁-C₆alkyl)-C₁-C₆alkyl-C(═O)—R₇,—O—C₁-C₂alkyl-C(═O)R₇, —C₁-C₆alkyl-S(═O)₂R₉, aryl, benzyl, heterocyclyl,aryloxy, benzyloxy, heterocyclyloxy; or aryl, benzyl, heterocyclyl,aryloxy, benzyloxy or heterocyclyloxy, which are independently of oneanother, depending on the substitution possibilities, mono- totrisubstituted in the ring by halogen, nitro, C₁-C₆alkyl, C₁-C₆alkoxy,C₁-C₆haloalkyl or C₁-C₆haloalkoxy;

R₆ is H, C₁-C₂₄alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂hydroxyalkyl, C₂-C₈alkenyl,C₂-C₈alkynyl, C₁-C₆alkoxy-C₁-C₆alkyl, Si(C₁-C₈alkyl)₃,C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₃-C₈Cycloalkoxy,C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl,C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy, (NR₈)₂,wherein the two R₈ are independent of each other, —C₁-C₆alkyl-C(═O)R₈,—C₁-C₆alkyl-S(═O)₂R₉, aryl, benzyl, heterocyclyl; or aryl, benzyl orheterocyclyl which, depending on the possibilities of substitution onthe ring, are mono- to trisubstituted by substituents selected from thegroup consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl,C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, Si(C₁-C₈alkyl)₃,C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy,C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl,C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy andC₁-C₁₂haloalkylthio;

R₇ is H, OH, C₁-C₂₄alkyl that is optionally substituted with OH, or—S(═O)₂—C₁-C₆alkyl; C₁-C₁₂alkenyl, C₂-C₁₂alkynyl, C₁-C₁₂alkoxy, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy, C₂-C₈alkenyloxy, aryl,aryloxy, benzyloxy, heterocyclyl, heterocyclyloxy or —N(R₈)₂, whereinthe two R₈ are independent of each other;

R₈H, C₁-C₆alkyl, which is optionally substituted with one to fivesubstituents selected from the group consisting of halogen, hydroxy,cyano C₁-C₆alkoxy, ═O, C₂-C₁₂alkenyl, C₂-C₁₂haloalkenyl,C₂-C₁₂haloalkynyl and C₃-C₁₂haloalkynyloxy; C₃-C₈-cycloalkyl, aryl,benzyl, heteroaryl; or aryl, benzyl or heteroaryl, which, depending onthe possibilities of substitution on the ring, are mono- totrisubstituted by substituents selected from the group consisting of OH,halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy,C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy,C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy, C₁-C₁₂alkylthio andC₁-C₁₂haloalkylthio;

R₉ is H, C₁-C₆alkyl, which is optionally substituted with one to fivesubstituents selected from the group consisting of halogen, C₁-C₆alkoxy,OH, ═O, C₂-C₁₂alkenyl, C₂-C₁₂haloalkenyl, C₂-C₁₂haloalkynyl,C₂-C₁₂haloalkynyl and cyano; aryl, benzyl, heteroaryl; or aryl, benzylor heteroaryl, which, depending on the possibilities of substitution onthe ring, are mono- to trisubstituted by substituents selected from thegroup consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl,Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy,C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy,C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy, C₁-C₁₂alkylthio andC₁-C₁₂haloalkylthio;

or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomerthereof;

a process for preparing these compounds, their isomers and tautomers andthe use of these compounds, their isomers and tautomers; pesticidalcompositions whose active compound is selected from these compounds andtheir tautomers; intermediates for the preparation of the said compoundsof the formula (I), methods for the preparation of the compounds of theformula (I), and a method for controlling pests using thesecompositions.

Hereinbefore and hereinafter, the configuration at the ε-position (4′-or 4″-position) of the compounds of the formulae (I) and (III) may be(S) as well as (R).

The literature proposes certain macrolide compounds for controllingpests. However, the biological properties of these known compounds arenot entirely satisfactory, and, as a consequence, there is still a needfor providing further compounds having pesticidal properties, inparticular for the control of insects and representatives of the orderAcarina. According to the invention, this object is achieved byproviding the present compounds of the formulae (I), (II) and (III).

The compounds claimed according to the invention are derivatives ofAvermectin. Avermectins are known to the person skilled in the art. Theyare a group of structurally closely related pesticidally activecompounds which are obtained by fermenting a strain of the microorganismStreptomyces avermitilis. Derivatives of Avermectins can be obtained byconventional chemical syntheses.

The Avermectins which can be obtained from Streptomyces avermitilis arereferred to as A1a, A1b, A2a, A2b, B1a, B1b, B2a and B2b. The compoundsreferred to as “A” and “B” have a methoxy radical and an OH group,respectively, in the 5-position. The “a” series and the “b” series arecompounds in which the substituent R₁ (in position 25) is a sec-butylradical and an isopropyl radical, respectively. The number 1 in the nameof the compounds means that carbon atoms 22 and 23 are linked by doublebonds; the number 2 means that they are linked by a single bond and thatthe C atom 23 carries an OH group. The above nomenclature is adhered toin the description of the present invention to denote the specificstructure type in the not naturally occurring Avermectin derivativesaccording to the invention which corresponds to the naturally occurringAvermectin. What is for instance claimed according to the invention arederivatives of compounds of the B1 series, in particular mixtures ofderivatives of Avermectin B1, especially B1a and B1b, along withderivatives having a single bond between carbon atoms 22 and 23, andderivatives having other substituents in the 25-position, as well as thecorresponding monosaccharides.

Some of the compounds of the formula (I) can be present as tautomers.Accordingly, hereinabove and hereinbelow, the compounds of the formula(I) are, if appropriate, also to be understood as including thecorresponding tautomers, even if the latter are not specificallymentioned in each case.

The compounds of formula (I) and, where applicable, their tautomers canform salts, for example acid addition salts. These acid addition saltsare formed, for example, with strong inorganic acids, such as mineralacids, for example sulfuric acid, a phosphoric acid or a hydrohalicacid, with strong organic carboxylic acids, such as unsubstituted orsubstituted, for example halo-substituted, C₁-C₄alkanecarboxylic acids,for example acetic acid, unsaturated or saturated dicarboxylic acids,for example oxalic acid, malonic acid, maleic acid, fumaric acid orphthalic acid, hydroxycarboxylic acids, for example ascorbic acid,lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid,or with organic sulfonic acids, such as unsubstituted or substituted,for example halo-substituted, C₁-C₄alkane- or aryl-sulfonic acids, forexample methane- or p-toluene-sulfonic acid. Compounds of formula (I)that have at least one acidic group can furthermore form salts withbases. Suitable salts with bases are, for example, metal salts, such asalkali metal salts or alkaline earth metal salts, for example sodium,potassium or magnesium salts, or salts with ammonia or with an organicamine, such as morpholine, piperidine, pyrrolidine, a mono-, di- ortri-lower alkylamine, for example ethylamine, diethylamine,triethylamine or dimethylpropylamine, or a mono-, di- ortrihydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine.Corresponding internal salts may also be formed where appropriate. Thefree form is preferred. Among the salts of the compounds of formula (I),the agrochemically advantageous salts are preferred. Hereinbefore andhereinafter, any reference to the free compounds of formula (I) or theirsalts is to be understood as including, where appropriate, also thecorresponding salts or the free compounds of formula (I), respectively.The same applies to tautomers of compounds of formula (I) and saltsthereof.

Unless defined otherwise, the general terms used hereinabove andhereinbelow have the meanings given below.

Unless defined otherwise, carbon-containing groups and compounds eachcontain from 1 up to and including 6, preferably from 1 up to andincluding 4, especially 1 or 2, carbon atoms.

Halogen—as a group per se and also as a structural element of othergroups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio—isfluorine, chlorine, bromine or iodine, in particular fluorine, chlorineor bromine, especially fluorine or chlorine.

Alkyl—as a group per se and also as a structural element of other groupsand compounds, such as haloalkyl, alkoxy and alkylthio—is, in each casetaking into account the number of carbon atoms contained in each case inthe group or compound in question, either straight-chain, i.e. methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, forexample isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentylor isohexyl.

Cycloalkyl—as a group per se and also as a structural element of othergroups and compounds, such as, for example, of halocycloalkyl,cycloalkoxy and cycloalkylthio is, in each case taking into account thenumber of carbon atoms contained in each case in the group or compoundin question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl.

Alkenyl—as a group per se and also as a structural element of othergroups and compounds—is, taking into account the number of carbon atomsand conjugated or isolated double bonds contained in the group, eitherstraight-chain, for example vinyl, allyl, 2-butenyl, 3-pentenyl,1-hexenyl, 1-heptenyl, 1,3-hexadienyl or 1,3-octadienyl, or branched,for example isopropenyl, isobutenyl, isoprenyl, tert-pentenyl,isohexenyl, isoheptenyl or isooctenyl. Preference is given to alkenylgroups having 3 to 12, in particular 3 to 6, especially 3 or 4, carbonatoms.

Alkynyl—as a group per se and also as a structural element of othergroups and compounds—is, in each case taking into account the number ofcarbon atoms and conjugated or isolated double bonds contained in thegroup or compound in question, either straight-chain, for exampleethynyl, propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl,3-hexen-1-ynyl or 1,5-heptadien-3-ynyl, or branched, for example3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2-ynyl or2-methylhept-3-ynyl. Preference is given to the group—CH₂—C₂-C₁₁alkynyl, in particular —CH₂—C₂-C₅alkynyl, especially—CH₂—C₂-C₃alkynyl.

Alkylene and alkenylene are straight-chain or branched bridge members;they are in particular —CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—,—CH₂—CH₂—CH₂—CH₂—CH₂—, —CH₂(CH₃)CH₂—CH₂—, —CH₂C(CH₃)₂—CH₂—, —CH₂—CH═CH—,—CH₂—CH═CH—CH₂ or —CH₂—CH═CH—CH₂—CH₂—.

Halogen-substituted carbon-containing groups and compounds, such as, forexample, halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyor alkylthio, can be partially halogenated or perhalogenated, where inthe case of polyhalogenation the halogen substituents can be identicalor different. Examples of haloalkyl—as a group per se and also as astructural element of other groups and compounds, such as haloalkoxy orhaloalkylthio—are methyl which is mono- to trisubstituted by fluorine,chlorine and/or bromine, such as CHF₂ or CF₃; ethyl which is mono- topentasubstituted by fluorine, chlorine and/or bromine, such as CH₂CF₃,CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF,CF₂CHBrF or CClFCHClF; propyl or isopropyl which is mono- toheptasubstituted by fluorine, chlorine and/or bromine, such asCH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF(CF₃)₂ or CH(CF₃)₂; butyl or oneof its isomers, mono- to nonasubstituted by fluorine, chlorine and/orbromine, such as CF(CF₃)CHFCF₃ or CH₂(CF₂)₂CF₃; pentyl or one of itsisomers, mono- to undecasubstituted by fluorine, chlorine and/orbromine, such as CF(CF₃)(CHF₂)CF₃ or CH₂(CF₂)₃CF₃; and hexyl or one ofits isomers, mono- to tridecasubstituted by fluorine, chlorine and/orbromine, such as (CH₂)₄CHBrCH₂Br, CF₂(CHF)₄CF₃, CH₂(CF₂)₄CF₃ orC(CF₃)₂(CHF)₂CF₃.

Aryl is in particular phenyl, naphthyl, anthracenyl, phenanthrenyl,perylenyl or fluorenyl, preferably phenyl.

Heterocyclyl is understood as being a three- to seven-memberedmonocyclic ring, which may be saturated or unsaturated, and thatcontains from one to three hetero atoms selected from the groupconsisting of N, O and S, especially N and S; or a bicyclic ring-systemhaving from 8 to 14 ring atoms, which may be saturated or unsaturated,and that may contain either in only one ring or in both ringsindependently of one another, one or two hetero atoms selected from N, Oand S.

Heterocyclyl is in particular piperidinyl, piperazinyl, oxiranyl,morpholinyl, thiomorpholinyl, pyridyl, N-oxidopyridinio, pyrimidyl,pyrazinyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl,dihydrofuranyl, tetrahydrofuranyl, pyranyl, tetrahydropyranyl, pyrrolyl,pyrrolinyl, pyrrolidinyl, pyrazolyl, imidazolyl, imidazolinyl,thiazolyl, isothiazolyl, triazolyl, oxazolyl, thiadiazolyl, thiazolinyl,thiazolidinyl, oxadiazolyl, phthalimidoyl, benzothienyl, quinolinyl,quinoxalinyl, benzofuranyl, benzimidazolyl, benzpyrrolyl, benzthiazolyl,indolinyl, isoindolinyl, cumarinyl, indazolyl, benzothiophenyl,benzofuranyl, pteridinyl or purinyl, which are preferably attached via aC atom; thienyl, benzofuranyl, benzothiazolyl, tetrahydropyranyl orindolyl is preferred; in particular pyridyl or thiazolyl. The saidheterocyclyl radicals may preferrably be unsubstituted or—depending onthe substitution possibilities on the ring system—substituted by 1 to 3substituents selected from the group consisting of halogen, ═O, —OH, ═S,SH, nitro, C₁-C₆alkyl, C₁-C₆hydroxyalkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl,C₁-C₆haloalkoxy, phenyl, benzyl, —C(═O)—R₆ and —CH₂—C(═O)—R₆.

In the context of the present invention, preference is given to

(2) compounds according to group (1) of the formula (I) in which R₁ isisopropyl or sec-butyl, preferably to those in which a mixture of theisopropyl and the sec-butyl derivative is present;

(3) compounds according to group (1) of the formula (I) in which R₁ iscyclohexyl;

(4) compounds according to group (1) of the formula (I) in which R₁ is1-methyl-butyl;

(5) compounds according to one of the groups (1) to (4) of the formula(I) in which the configuration at the ε-position is (R);

(6) compounds according to one of the groups (1) to (4) of the formula(I) in which the configuration at the ε-position is (S);

(7) compounds according to one of the groups (1) to (6) of the formula(I) in which n is 1;

(8) compounds according to one of the groups (1) to (6) of the formula(I) in which n is 0;

(9) compounds according to one of the groups (1) to (8) of the formula(I) in which X—Y is —CH═CH—;

(10) compounds according to one of the groups (1) to (8) of the formula(I) in which X—Y is —CH₂—CH₂—;

(11) compounds according to one of the groups (1) to (10) of the formula(I) in which U is —N(R₂)—O(R₃)

(12) compounds according to one of the groups (1) to (10) of the formula(I) in which U is —N⁺(O⁻)═C(R_(Z))(R_(E))

(13) compounds according to group (11) of the formula (I) in which R₃ is—Q, —C(═O)—Z—Q or —CN and R₂ is independently taken from —Q;

(14) compounds according to group (11) of the formula (I) in which R₃ is—Q, —C(═O)—Z—Q or —CN and R₂ is independently taken from —C(═O)—Z—Q;

(15) compounds according to group (11) of the formula (I) in which R₃ is—Q, —C(═O)—Z—Q or —CN and R₂ is —CN;

(16) compounds according to group (11) of the formula (I) in which R₂ isQ, —C(═O)—Z—Q or —CN and R₃ is independently taken from —Q;

(17) compounds according to group (11) of the formula (I) in which R₂ is—Q, —C(═O)—Z—Q or —CN and R₃ is independently taken from —C(═O)—Z—Q;

(18) compounds according to group (11) of the formula (I) in which R₂ is—Q, —C(═O)—Z—Q or —CN and R₃ is —CN;

(19) compounds according to one of the groups (13) to (18) of theformula (I) in which Z is a bond;

(20) compounds according to one of the groups (13) to (18) of theformula (I) in which Z is O;

(21) compounds according to one of the groups (13) to (18) of theformula (I) in which Z is —NR₄—;

(22) compounds according to group (11) of the formula (I) in which R₂and R₃together are a three membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(23) compounds according to group (11) of the formula (I) in which R₂and R₃together are a four membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(24) compounds according to group (11) of the formula (I) in which R₂and R₃ together are a five membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(25) compounds according to group (11) of the formula (I) in which R₂and R₃together are a six membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(26) compounds according to group (11) of the formula (I) in which R₂and R₃together are a seven membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(27) compounds according to group (11) of the formula (I) in which R₂and R₃together are a three membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(28) compounds according to group (11) of the formula (I) in which R₂and R₃ together are a four membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(29) compounds according to group (11) of the formula (I) in which R₂and R₃ together are a five membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(30) compounds according to group (11) of the formula (I) in which R₂and R₃ together are a six membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(31) compounds according to group (11) of the formula (I) in which R₂and R₃together are a seven membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(32) compounds according to group (12) of the formula (I) in which R_(E)is —Q, —C(═O)—Z—Q or —CN and R_(Z) is independently taken from —Q;

(33) compounds according to group (12) of the formula (I) in which R_(E)is —Q. —C(═O)—Z—Q or —CN and R_(Z) is independently taken from—C(═O)—Z—Q;

(34) compounds according to group (12) of the formula (I) in which R_(E)is —Q, —C(═O)—Z—Q or —ON and R_(Z) is —ON;

(35) compounds according to group (12) of the formula (I) in which R_(Z)is —Q, —C(═O)—Z—Q or —CN and R_(E) is independently taken from —Q;

(36) compounds according to group (12) of the formula (I) in which R_(Z)is Q, —C(═O)—Z—Q or —ON and R_(E) is independently taken from—C(═O)—Z—Q;

(37) compounds according to group (12) of the formula (I) in which R_(Z)is —Q, —C(═O)—Z—Q or —ON and R_(E) is —CN;

(38) compounds according to one of the groups (32) to (37) of theformula (I) in which Z is a bond;

(39) compounds according to one of the groups (32) to (37) of theformula (I) in which Z is O;

(40) compounds according to one of the groups (32) to (37) of theformula (I) in which Z is —NR₄—;

(41) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a three membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(42) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a four membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(43) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a five membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(44) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a six membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(45) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a seven membered alkylene bridge, which isunsubstituted or mono- to tri-substituted;

(46) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a three membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(47) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a four membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(48) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a five membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(49) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a six membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted;

(50) compounds according to group (12) of the formula (I) in which R_(Z)and R_(E) together are a seven membered alkenylene bridge, which isunsubstituted or mono- to tri-substituted.

Special preference is given within the scope of the invention to thecompounds of formula (I) listed in Tables A1 to A8 and in Tables 1 to 48and, where applicable, their tautomers, their mixtures of tautomers,their E/Z isomers and mixtures of E/Z isomers.

The invention also provides a process for preparing the compounds of theformula (I) and, if appropriate, tautomers thereof, wherein

(A) for the preparation of a compound of the formula (I) as definedunder (1), wherein U is —NHOR₃ and R₃ has the same meanings as givenunder (1) for formula (I), a compound of the formula

in which G is H or a protecting group, n, X—Y, R₁ and R₃ have the samemeanings as given above under (1) for formula (I), is treated with areducing agent; or

(B) for the preparation of a compound of the formula

wherein G is H or a protecting group, n, X—Y, R₁, R_(E) and R_(Z) havethe same meanings as given above under (1) for formula (I), a compoundof the formula

in which G is H or a protecting group, R₂ and R₃ are H, and n, X—Y andR₁ have the same meanings as given above under (1) for formula (I), isreacted with a compound of the formula R_(E)—C(═O)—R_(Z), in which R_(E)and R_(Z) have the same meanings as given above under (1) for formula(I); or

(C) for the preparation of a compound of the formula (Ia) as definedabove under (B), a compound of the formula

in which n, X—Y, R₁, R_(E) and R_(Z) have the same meanings as givenabove under (1) for formula (I), is treated with an oxidating agent; or

(D) for the to preparation of a compound of the formula (Ib) as definedabove under (B), wherein R₂ and R₃ are H, a compound of the formula (Ia)as defined above under (B), is reacted with a compound of the formulaQ₁-O—NH₂, in which Q₁ is H, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl,C₃-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, aryl or heterocyclyl, which areunsubstituted or mono- to pentasubstituted, and wherein the substituentsof the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl andheterocyclyl radicals mentioned have the same meaning as given aboveunder (1) for formula (I); or

(E) for the preparation of a compound of the formula

in which G is H or a protecting group, n, X—Y, R₁, R_(E) and R_(Z) havethe same meanings as given above under (1) for formula (I), a compoundof the formula (Ia) as defined above under (B) is reacted with areducing agent; or

(F) for the preparation of a compound of the formula

in which G is H or a protecting group, n, X—Y, R₁, R_(E) and R_(Z) havethe same meanings as given above under (1) for formula (I), and Q₂ is H,C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂cycloalkyl,C₅-C₁₂-cycloalkenyl, aryl or heterocyclyl, which are unsubstituted ormono- to pentasubstituted, and wherein the substituents of the alkyl,alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclylradicals mentioned have the same meaning as given above under (1) forformula (I);

a compound of the formula (Ia) as defined above under (B) is reactedwith a compound Q₂—M or a compound, wherein Q₂—M—X₁, both in which Q₂has the same meaning as given above and M is lithium, magnesium or zinc,and X₁ is chloride, bromide, iodide or trifluoro-methanesulfonate; or

(G) for the preparation of a compound of the formula

in which G is H or a protecting group, n, X—Y, R₁, R_(E) and R_(Z) havethe same meanings as given above under (1) for formula (I), and in whichQ₃ and Q₄ are, independently from each other, H, C₁-C₁₂alkyl,C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂-cycloalkyl, C₅-C₁₂cycloalkenyl,aryl or heterocyclyl, which are unsubstituted or mono- topentasubstituted, and wherein the substituents of the alkyl, alkenyl,alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclyl radicalsmentioned have the same meaning as given above under (1) for formula(I);

a compound of the formula (Ia) as defined above under (B) is reactedwith a compound Q₃—C≡C—Q₄, in which Q₃ and Q₄ have the same meaning asgiven above; or

(H) for the preparation of a compound of the formula

in which G is H or a protecting group, n, X—Y, R₁, R_(E) and R_(Z) havethe same meanings as given above under (1) for formula (I), and in whichQ₅, Q₆, Q₇ and Q₈ are, independently from each other, H, C₁-C₁₂alkyl,C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, arylor heterocyclyl, which are unsubstituted or mono- to pentasubstituted,and wherein the substituents of the alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkenyl, aryl and heterocyclyl radicals mentioned have the samemeaning as given above under (1) for formula (I);

a compound of the formula (Ia) as defined above under (B) is reactedwith a compound Q₅Q₆C═CQ₇Q₈, in which Q₅, Q₆, Q₇ and Q₈ have the samemeaning as given above under (H) for formula (If); or

(J) for the preparation of a compound of the formula (Ib) a definedabove under (B), in which R₂ and R₃ have the same meanings as givenabove under (1) for formula (I),

a compound of the formula (Ib) as defined above under (B), wherein R₂ isH and R₃ is as defined under (1) for formula (I), is reacted with acompound Q—X₂, with a compound Q—C(═O)—Cl, with a compound Q—O—C(═O)—Cl,with a compound Q—N═C═O or with a compound in which Q has the samemeaning as given above under (1) for formula (I) and X₂ is chloride,bromide, iodide, alkylsulfonate, haloalkylsulfonate or arylsulfonate; or

(K) for the preparation of a compound of the formula (Ib) as definedabove under (B), and wherein R₂ and R₃ have the same meanings as givenabove under (1) for formula (I), a compound of the formula (Ib) asdefined above under (B), wherein R₂ has the same meanings as given aboveunder (1) for formula (I) and R₃ is H, is reacted with a compound Q—X₂,wherein X₂ is chloride, bromide, iodide, alkylsulfonate,haloalkylsulfonate or arylsulfonate, or with a compound Q—C(═O)—Cl, witha compound Q—O—C(═O)—Cl or with a compound Q—N═C═O, in which Q has thesame meaning as given above under (1) for formula (I); or

(L) for the preparation of a compound of the formula (I)

in which G is H or a protecting group, n, X—Y, R₁ and R₃ have the samemeanings as given above under (1) for formula (I), X₃ is —CN or —CO—Q₁₂or —CO—O—Q₁₂, and Q₉, Q₁₀, Q₁₁ and Q₁₂ are, independently from eachother, H, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂cycloalkyl,C₅-C₁₂cycloalkenyl, aryl or heterocyclyl, which are unsubstituted ormono- to pentasubstituted, and wherein the substituents of the alkyl,alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclylradicals mentioned have the same meaning as given above under (1) forformula (I);

a compound of the formula (Ib), as defined above under (B), in which R₂is H and and R₃ has the same meanings as given above under (1) forformula (I), is reacted with a compound Q₁₀Q₁₁C═CQ₉X₃, in which Q₉, Q₁₀,Q₁₁ and X₃ have the same meaning as given above under (L) for formula(I);

and in each case of variants (A) to (L), if required for the synthesisof a compound of the formula (I), wherein the substituent in the5-position is OH, the protecting group is removed.

The compounds of formulae (II) and of formula (III) are new, and arealso an aspect of the invention. They are valuable intermediates for thesynthesis of compounds of formula (I), and can be prepared by methodsknown per se. Surprisingly, they are also valuable pesticides. The useof the compounds of formula (II) and of formula (III), and of thecompounds of the formula (I) having in the 5-position a protectinggroup, for the synthesis of compounds of formula (I), a method forcontrolling pests with the said compounds of the formulae (II) and(III), and pesticidal compositions containing them are also subjects ofthis invention. The preferences for the substituents are the same asdefined for the compound of the formula (I) in (2) to (50). Thecompounds of the formula (I), (II) and (III) wherein the group G in the5-position is H are preferred.

The comments made above in connection with tautomers of compounds offormula (I) apply analogously to the starting materials andintermediates mentioned hereinabove and hereinbelow in respect of theirtautomers.

Compounds of formula (I) bearing a functional group in its free orprotected form can be used as starting materials for the preparation offurther compounds of formula (I). For such manipulations methods knownto the person skilled in the art can be applied.

For example a compound of formula (I) wherein Q is CH₂CH₂OC(═O)CH₃ canbe converted to a compound of formula (I) wherein Q is CH₂CH₂OH. Furtherstandard reactions can deliver compounds of formula (I) wherein Q is—CH₂CH₂OCH₂O-Alkyl or —CH₂CH₂N₃. A compound of formula (I) wherein Q is—CH₂CH₂N₃ can be converted to a compound of formula (I) wherein Q is—CH₂CH₂NH₂. Treatment of such a compound of formula (I) for instancewith Hal-C(═O)R₅, gives compounds of formula (I) wherein Q is—CH₂CH₂NHCOR₅.

The reactions described hereinabove and hereinbelow are carried out in amanner known per se, for example in the absence or, customarily, in thepresence of a suitable solvent or diluent or of a mixture thereof, thereactions being carried out, as required, with cooling, at roomtemperature or with heating, for example in a temperature range ofapproximately from −80° C. to the boiling temperature of the reactionmedium, preferably from approximately 0° C. to approximately +150° C.,and, if necessary, in a closed vessel, under pressure, under an inertgas atmosphere and/or under anhydrous conditions. Especiallyadvantageous reaction conditions can be found in the Examples.

The reaction time is not critical; a reaction time of from about 0.1 toabout 24 hours, especially from about 0.5 to about 10 hours, ispreferred.

The product is isolated by customary methods, for example by means offiltration, crystallization, distillation or chromatography, or anysuitable combination of such methods.

The starting materials mentioned hereinabove and hereinbelow that areused for the preparation of the compounds of formula (I) and, whereapplicable, their tautomers can be prepared by methods known per se,e.g. as indicated below.

Protecting groups G in the compounds of formulae (I), (II) and (III)include: alkyl ether radicals, such as methoxymethyl, methylthiomethyl,tert-butylthiomethyl, benzyloxymethyl, p-methoxybenzyl,2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl,2-(trimethylsilyl)ethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl,1-ethoxyethyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl,1-methyl-1-benzyloxyethyl, trichloroethyl, 2-trimethylsilylethyl,tert-butyl, allyl, p-methoxyphenyl, 2,4-dinitrophenyl, benzyl,p-methoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, triphenylmethyl;trialkylsilyl radicals, such as trimethylsilyl, triethylsilyl,dimethyl-tert-butylsilyl, dimethyl-isopropylsilyl,dimethyl-1,1,2-trimethylpropylsilyl, diethyl-isopropylsilyl,dimethyl-tert-hexylsilyl, but also phenyl-tert-alkylsilyl groups, suchas diphenyl-tert-butylsilyl; esters, such as formates, acetates,chloroacetates, dichloroacetates, trichloroacetates, trifluoroacetates,methoxyacetates, phenoxyacetates, pivaloates, benzoates; alkylcarbonates, such as methyl-, 9-fluorenylmethyl-, ethyl-,2,2,2-trichloroethyl-, 2-(trimethylsilyl)ethyl-, vinyl-, allyl-,benzyl-, p-methoxybenzyl-, o-nitrobenzyl-, p-nitrobenzyl-, but alsop-nitrophenyl-carbonate.

Preference is given to trialkylsilyl radicals, such as trimethylsilyl,triethylsilyl, dimethyl-tert-butylsilyl, diphenyl-tert-butylsilyl,esters, such as methoxyacetates and phenoxyacetates, and carbonates,such as 9-fluorenylmethylcarbonates and allylcarbonates.Dimethyl-tert-butylsilyl ether is especially preferred.

There are suitable for the removal of the protecting group Lewis acids,such as hydrochloric acid, methanesulfonic acid, BF₃*OEt₂, HF inpyridine, Zn(BF₄)₂*H₂O, p-toluenesulfonic acid, AlCl₃, HgCl₂; ammoniumfluoride, such as tetrabutylammonium fluoride; bases, such as ammonia,trialkylamine or heterocyclic bases; hydrogenolysis with a catalyst,such as palladium-on-carbon; reducing agents, such as sodium borohydrideor tributyltin hydride with a catalyst, such as Pd(PPh₃)₄, or also zincwith acetic acid.

Preference is given to acids, such as methanesulfonic acid or HF inpyridine; sodium borohydride with Pd(0); bases, such as ammonia,triethylamine or pyridine; especially acids, such as HF in pyridine ormethanesulfonic acid.

Process Variant (A):

Examples of solvents and diluents include: aromatic, aliphatic andalicyclic hydro-carbons and halogenated hydrocarbons, such as benzene,toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene,bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,trichloromethane, tetrachloromethane, dichloroethane, trichloroethene ortetrachloroethene; ethers, such as diethyl ether, dipropyl ether,diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyleneglycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran ordioxane; alcohols, such as methanol, ethanol, propanol, isopropanol,butanol, ethylene glycol or glycerol; carboxylic acids, such as aceticacid, pivalic acid or formic acid; ketones, such as acetone, methylethyl ketone or methyl isobutyl ketone; carboxylic acid esters, such asmethyl acetate, ethyl acetate, or esters of benzoic acid; amides, suchas N,N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide,N-methyl-pyrrolidone or hexamethylphosphoric acid triamide; nitriles,such as acetonitrile or propionitrile; and sulfoxides, such as dimethylsulfoxide; and also water; or mixtures of the mentioned solvents;especially suitable are ethers, alcohols, water, carboxylic acids, ormixtures thereof, more especially tetrahydrofuran, pivalic acid orwater.

The reactions are advantageously carried out in a temperature range offrom about room temperature to the boiling point of the solvent used;preference being given to reaction at 10 to 30° C.

Examples of reducing agents are known to a person skilled in the art,they include hydrides; especially suitable are borohydrides, for examplesodium borohydride or sodium cyanoborohydride.

In a preferred embodiment of Variant (A) the reaction is carried outwith sodium cyanoborohydride at room temperature, in tetrahydrofuran inthe presence of pivalic acid and water.

Especially preferred conditions for this Process variant are describedin Examples A1.1, A1.2, A5.1 and A6.1.

Process Variant (B):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are esters, water or mixturesthereof, or the use of no solvent.

The reactions are advantageously carried out in a temperature range offrom about room temperature to the boiling point of the solvent used;preference being given to reaction at 10 to 30° C.

Examples of a compound R_(E)—C(═O)—R_(Z) include ketones or aldehydes,for example formaldehyde, acetaldehyde, benzaldehyde or acetone.

In a preferred embodiment of Variant (B) the reaction is carried outwith the compound R_(E)—C(═O)—R_(Z) as the solvent.

In another preferred embodiment of Variant (B) the reaction is carriedout with the compound R_(E)—C(═O)—R_(Z) in a mixture of ethyl acetateand water.

Especially preferred conditions for this Process variant are described,for example, in Examples A7.1 and A7.2.

Process Variant (C):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are halogenated hydrocarbons,for example dichloromethane or trichloromethane.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably from 0°C. to room temperature.

Examples of oxidating agents are known to a person skilled in the art,they include, for example, inorganic salts, for example sodium periodateor potassium permanganate; oxides, for example selenium dioxide ormercury oxide; peroxides, for example hyrogenperoxide ordimethyldioxirane; or peracids; especially suitable are peracids, forexample 3-chloroperbenzoic acid or peracetic acid.

Especially preferred conditions for this Process variant are described,for example, in Example A8.1.

Process Variant (D):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are alcohols, for exampleethanol, methanol or iso-propanol.

Process Variant (D):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are alcohols, for exampleethanol, methanol or iso-propanol.

The reactions are advantageously carried out in a temperature range ofapproximately from room temperature to the boiling point of the solventused.

Examples of a compound Q₁-O—NH₂ include N-unsubstituted hydroxylamines,for example O-methylhydroxylamine, O-phenylhydroxylamine orhydroxylamine.

In a preferred embodiment of Variant (D) the reaction is carried outwith hydroxylamine hydrochloride, in the presence of sodium bicarbonate,at 60° C. in methanol as the solvent.

Especially preferred conditions for this Process variant are described,for example, in Example A4.1.

Process Variant (E):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are ethers, alcohols, water,carboxylic acids, or mixtures thereof, more especially tetrahydrofuran,acetic acid or water.

The reactions are advantageously carried out in a temperature range offrom about room temperature to the boiling point of the solvent used;preference being given to reaction at 10 to 30° C.

Examples of reducing agents are known to a person skilled in the art,they include hydrides; especially suitable are borohydrides, for examplesodium borohydride or sodium cyanoborohydride.

In a preferred embodiment of Variant (E) the reaction is carried outwith sodium cyanoborohydride at room temperature, in tetrahydrofuran asthe solvent.

Especially preferred conditions for this Process variant are described,for example, in Example A2.1.

Process Variant (F):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are ethers, for example diethylether or tetrahydrofuran.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably at roomtemperature.

Especially preferred conditions for this Process variant are described,for example, in Examples A2.2, A2.3 and A2.6.

Process Variant (G):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are ethers, for example diethylether or tetrahydrofuran, or aromatic hydrocarbons such as benzene,toluene or xylene, or the use of no solvent.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably from 0°C. to 80° C.

In a preferred embodiment of Variant (G) the reaction is carried out at0° C., in tetrahydrofuran as the solvent.

Especially preferred conditions for this Process variant are described,for example, in Example A3.2.

Process Variant (H):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are ethers, for example diethylether or tetrahydrofuran, or aromatic hydrocarbons such as benzene,toluene or xylene, or the use of no solvent.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably from 0°C. to 80° C.

In a preferred embodiment of Variant (H) the reaction is carried out at80° C., in toluene as the solvent.

Especially preferred conditions for this Process variant are described,for example, in Example A3.1.

Process Variant (J):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are hydrocarbons, aromatichydrocarbons, halogenated hydrocarbons, esters or ethers, for examplehexane, toluene, dichloromethane, ethyl acetate or tetrahydrofuran; orwater; or mixtures thereof.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably from 0°C. to room temperature; in the presence of a base, for example aninorganic base, such as sodium hydroxide, potassium hydroxide, sodiumcarbonate or sodium bicarbonate, or an organic base, such as pyridine,triethylamine or N-ethyl-N,N-diisopropylamine; or without the presenceof a base.

In a preferred embodiment of Variant (J) the reaction is carried out inthe presence of bicarbonate at room temperature, in a mixture of ethylacetate and water as the solvent.

In another preferred embodiment of Variant (J) the reaction is carriedout without a base at room temperature, in ethyl acetate as the solvent.

Especially preferred conditions for this Process variant are described,for example, in Examples A1.3, A1.4 and A2.4.

Process Variant (K):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are hydrocarbons, aromatichydrocarbons, halogenated hydrocarbons, esters or ethers, for examplehexane, toluene, dichloromethane, ethyl acetate or tetrahydrofuran; orwater; or mixtures thereof.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably from 0°C. to room temperature; in the presence of a base, for example aninorganic base, such as sodium hydroxide, potassium hydroxide, sodiumcarbonate or sodium bicarbonate, or an organic base, such as pyridine,triethylamine or N-ethyl-N,N-diisopropylamine; or without the presenceof a base.

In a preferred embodiment of Variant (K) the reaction is carried out inthe presence of bicarbonate at room temperature, in a mixture of ethylacetate and water as the solvent.

In another preferred embodiment of Variant (K) the reaction is carriedout without a base at room temperature, in ethyl acetate as the solvent.

Especially preferred conditions for this Process variant are described,for example, in Examples A2.7 and A2.8.

Process Variant (L):

Examples of solvents and diluents include those listed above underProcess variant (A); especially suitable are ethers, for example diethylether or tetrahydrofuran, or aromatic hydrocarbons such as benzene,toluene or xylene, or the use of no solvent.

The reactions are advantageously carried out in a temperature range offrom 0° C. to the boiling point of the solvent used, preferably from 0°C. to 80° C.

In a preferred embodiment of Variant (L) the reaction is carried out atroom temperature, without the use of a solvent.

Especially preferred conditions for this Process variant are described,for example, in Example A2.5.

The compounds of formula (I) may be in the form of one of the possibleisomers or in the form of a mixture thereof, in the form of pure isomersor in the form of an isomeric mixture, i.e. in the form of adiastereomeric mixture; the invention relates both to the pure isomersand to the diastereomeric mixtures and is to be interpreted accordinglyhereinabove and hereinbelow, even if stereochemical details are notmentioned specifically in every case.

The diastereomeric mixtures can be resolved into the pure isomers byknown methods, for example by recrystallisation from a solvent, bychromatography, for example high pressure liquid chromatography (HPLC)on acetylcellulose, with the aid of suitable micro-organisms, bycleavage with specific, immobilised enzymes, or via the formation ofinclusion compounds, for example using crown ethers, only one isomerbeing complexed.

Apart from by separation of corresponding mixtures of isomers, purediastereoisomers can be obtained according to the invention also bygenerally known methods of stereoselective synthesis, for example bycarrying out the process according to the invention using startingmaterials having correspondingly suitable stereochemistry.

In each case it is advantageous to isolate or synthesise thebiologically more active isomer, where the individual components havedifferent biological activity.

The compounds of formula (I) may also be obtained in the form of theirhydrates and/or may include other solvents, for example solvents whichmay have been used for the crystallisation of compounds in solid form.

The invention relates to all those embodiments of the process accordingto which a compound obtainable as starting material or intermediate atany stage of the process is used as starting material and all or some ofthe remaining steps are carried out, or in which a starting material isused in the form of a derivative and/or a salt and/or its diastereomers,or, especially, is formed under the reaction conditions. For instancecompounds of formula (I) bearing a functional group or a protectinggroup, preferably in the 5-position, can be used as starting materialsfor the preparation of further compounds of formula (I). For suchmanipulations methods known to the person skilled in the art can beapplied.

In the processes of the present invention it is preferable to use thosestarting materials and intermediates which result in the compounds offormula (I) that are especially preferred.

The invention relates especially to the preparation processes describedin Examples A1.1 to A8.1.

In the area of pest control, the compounds of formula (I) according tothe invention are active ingredients exhibiting valuable preventiveand/or curative activity with a very advantageous biocidal spectrum anda very broad spectrum, even at low rates of concentration, while beingwell tolerated by warm-blooded animals, fish and plants. They are,surprisingly, equally suitable for controlling both plant pests andecto- and endo-parasites in humans and more especially in productivelivestock, domestic animals and pets. They are effective against all orindividual development stages of normally sensitive animal pests, butalso of resistant animal pests, such as insects, preferably of theorders Lepidoptera; Coleoptera, Homoptera, Orthoptera, Isoptera,Psocoptera, Anoplura, Mallophaga, Thysanoptera; Heteroptera,Siphonaptera, Hymentoptera and Thysanura, and representatives of theorder Acarina, nematodes, cestodes and trematodes, while at the sametime protecting useful organisms. The said animal pests especiallyinclude, for example, those mentioned in European Patent ApplicationEP-A-736 252, page 5, line 55, to page 6, line 55. The pests mentionedtherein are therefore included by reference in the subject matter of thepresent invention.

The insecticidal or acaricidal activity of the active ingredientsaccording to the invention may manifest itself directly, i.e. in themortality of the pests, which occurs immediately or only after sometime, for example during moulting, or indirectly, for example in reducedoviposition and/or hatching rate, good activity corresponding to amortality of at least 50 to 60%.

It is also possible to control pests of the class Nematoda using thecompounds according to the invention. Such pests include, for example,root knot nematodes, cyst-forming nematodes and also stem and leafnematodes;

especially of Heterodera spp., e.g. Heterodera schachtii, Heterodoraavenae and Heterodora trifolii; Globodera spp., e.g. Globoderarostochiensis; Meloidogyne spp., e.g. Meloidogyne incognita andMeloidogyne javanica; Radopholus spp., e.g. Radopholus simiis;Pratylenchus, e.g. Pratylenchus neglectans and Pratylenchus penetrans;Tylenchulus, e.g. Tylenchulus semipenetrans; Longidorus, Trichodorus,Xiphinema, Ditylenchus, Apheenchoides and Anguina; insbesondereMeloidogyne, e.g. Meloidogyne incognita, and Heterodera, e.g. Heteroderaglycines.

An especially important aspect of the present invention is the use ofthe compounds of formula (I) according to the invention in theprotection of plants against parasitic feeding pests.

The compounds according to the invention can be used to control, i.e. toinhibit or destroy, pests of the mentioned type occurring on plants,especially on useful plants and ornamentals in agriculture, inhorticulture and in forestry, or on parts of such plants, such as thefruits, blossoms, leaves, stems, tubers or roots, while in some casesplant parts that grow later are still protected against those pests.

Target crops include especially cereals, such as wheat, barley, rye,oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet;fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears,plums, peaches, almonds, cherries and berries, e.g. strawberries,raspberries and blackberries; leguminous plants, such as beans, lentils,peas and soybeans; oil plants, such as rape, mustard, poppy, olives,sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae,such as marrows, cucumbers and melons; fibre plants, such as cotton,flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruitand mandarins; vegetables, such as spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae,such as avocado, cinnamon and camphor; and tobacco, nuts, coffee,aubergines, sugar cane, tea, pepper, vines, hops, bananas, naturalrubber plants and ornamentals.

Further areas of use of the compounds according to the invention are theprotection of stored goods and storerooms and the protection of rawmaterials, and also in the hygiene sector, especially the protection ofdomestic animals and productive livestock against pests of the mentionedtype, more especially the protection of domestic animals, especiallycats and dogs, from attack by fleas, ticks and nematodes.

The invention therefore relates also to pesticidal compositions, such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, wettablepowders, soluble powders, dispersible powders, wettable powders, dusts,granules and encapsulations of polymer substances, that comprise atleast one of the compounds according to the invention, the choice offormulation being made in accordance with the intended objectives andthe prevailing circumstances.

The active ingredient is used in those compositions in pure form, asolid active ingredient, for example, in a specific particle size, orpreferably together with at least one of the adjuvants customary informulation technology, such as extenders, e.g. solvents or solidcarriers, or surface-active compounds (surfactants). In the area ofparasite control in humans, domestic animals, productive livestock andpets it will be self-evident that only physiologically tolerableadditives are used.

As formulation adjuvants there are used, for example, solid carriers,solvents, stabilisers, “slow release” adjuvants, colouringsi andoptionally surface-active substances (surfactants). Suitable carriersand adjuvants include all substances customarily used. As adjuvants,such as solvents, solid carriers, surface-active compounds, non-ionicsurfactants, cationic surfactants, anionic surfactants and furtheradjuvants in the compositions used according to the invention, therecome into consideration, for example, those described in EP-A-736 252,page 7, line 51 to page 8, line 39.

The compositions for use in crop protection and in humans, domesticanimals and productive livestock generally comprise from 0.1 to 99%,especially from 0.1 to 95%, of active ingredient and from 1 to 99.9%,especially from 5 to 99.9%, of at least one solid or liquid adjuvant,the composition generally including from 0 to 25%, especially from 0.1to 20%, of surfactants (% is percent by weight in each case). Whereascommercial products will preferably be formulated as concentrates, theend user will normally employ dilute formulations having considerablylower concentrations of active ingredient.

The action of the compounds according to the invention and thecompositions comprising them against animal pests can be significantlybroadened and adapted to the given circumstances by the addition ofother insecticides, acaricides or nematicides. Suitable additivesinclude, for example, representatives of the following classes of activeingredient: organophosphorus compounds, nitrophenols and derivatives,formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbonsand Bacillus thuringiensis preparations.

Examples of especially suitable mixing partners include: azamethiphos;chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine;diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil;fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene;lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon;profenofos; diofenolan; a compound obtainable from the Bacillusthuringiensis strain GC91 or from strain NCTC11821; pymetrozine;bromopropylate; methoprene; disulfoton; quinalphos; taufluvalinate;thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb;bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap;chlorfluazuron; chlorpyrifos; clothianidin; cyfluthrin;lambda-cyhalothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin;diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb;fenvalerate; formothion; methiocarb; heptenophos; imidacloprid;isoprocarb; methamidophos; methomyl; mevinphos; parathion;parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron;terbufos; triazamate; fenobucarb; tebufenozide; fipronil;beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; pyridalyl;fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid;emamectin; emamectin-benzoate; spinosad; a plant extract that is activeagainst insects; a preparation that comprises nematodes and is activeagainst insects; a preparation obtainable from Bacillus subtilis; apreparation that comprises fungi and is active against insects; apreparation that comprises viruses and is active against insects;chlorfenapyr; acephate; acrinathrin; alanycarb; alphamethrin; amitraz;AZ 60541; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap;beta-cyfluthrin; brofenprox; bromophos A; bufencarb; butocarboxin;butylpyridaben; cadusafos; carbaryl; carbophenothion; chloethocarb;chlorethoxyfos; chlormephos; cis-resmethrin; clocythrin; clofentezine;cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S;demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate;dimethylvinphos; dioxathion; edifenphos; esfenvalerate; ethion;ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatin oxide;fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam;flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos;fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; flonicamid;iprobenfos; isofenphos; isoxathion; ivermectin; malathion; mecarbam;mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC184; nithiazine; omethoate; oxamyl; oxydemethon M; oxydeprofos;permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M;pirimiphos E; promecarb; propaphos; prothiofos; prothoate; pyrachlophos;pyradaphenthion; pyresmethrin; pyrethrum; tebufenozide; salithion;sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin;temephos; terbam; tetrachlorvinphos; thiacloprid; thiafenox;thiamethoxam; thiodicarb; thiofanox; thionazin; thuringiensin;tralomethrin; triarathene; triazophos; triazuron; trichlorfon;triflumuron; trimethacarb; vamidothion; xylylcarb; etoxazole;zetamethrin; indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylylmethylcarbamate); or the fungus pathogen Metarhizium anisopliae.

Preferred crop protection products have especially the followingcompositions (% is percent by weight):

Emulsifiable Concentrates:

active ingredient: 1 to 90%, preferably 5 to 20%

surfactant: 1 to 30%, preferably 10 to 20%

solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surfactant: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surfactant: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 99%, preferably 15 to 98%

Granules:

active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The compositions according to the invention may also comprise furthersolid or liquid adjuvants, such as stabilisers, e.g. vegetable oils orepoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil orsoybean oil), antifoams, e.g. silicone oil; preservatives, viscosityregulators, binders and/or tackifiers as well as fertilisers or otheractive ingredients for obtaining special effects, e.g. acaricides,bactericides, fungicides, nematicides, molluscicides or selectiveherbicides.

The crop protection products according to the invention are prepared inknown manner, in the absence of adjuvants, e.g. by grinding, sievingand/or compressing a solid active ingredient or mixture of activeingredients, for example to a certain particle size, and in the presenceof at least one adjuvant, for example by intimately mixing and/orgrinding the active ingredient or mixture of active ingredients with theadjuvant(s). The invention relates likewise to those processes for thepreparation of the compositions according to the invention and to theuse of the compounds of formula (I) in the preparation of thosecompositions.

The invention relates also to the methods of application of the cropprotection products, i.e. the methods of controlling pests of thementioned type, such as spraying, atomising, dusting, coating, dressing,scattering or pouring, which are selected in accordance with theintended objectives and the prevailing circumstances, and to the use ofthe compositions for controlling pests of the mentioned type. Typicalrates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to500 ppm, of active ingredient. The rates of application per hectare aregenerally from 1 to 2000 g of active ingredient per hectare, especiallyfrom 10 to 1000 g/ha, preferably from 20 to 600 g/ha, more especiallyfrom 20 to 600 g/ha.

A preferred method of application in the area of crop protection isapplication to the foliage of the plants (foliar application), thefrequency and the rate of application being dependent upon the risk ofinfestation by the pest in question. However, the active ingredient canalso penetrate the plants through the roots (systemic action) when thelocus of the plants is impregnated with a liquid formulation or when theactive ingredient is incorporated in solid form into the locus of theplants, for example into the soil, e.g. in granular form (soilapplication). In the case of paddy rice crops, such granules may beapplied in metered amounts to the flooded rice field.

The crop protection products according to the invention are alsosuitable for protecting plant propagation material, e.g. seed, such asfruits, tubers or grains, or plant cuttings, including propagationmaterial of genetically modified plants, against animal pests. Thepropagation material can be treated with the composition beforeplanting: seed, for example, can be dressed before being sown. Theactive ingredients according to the invention can also be applied tograins (coating), either by impregnating the seeds in a liquidformulation or by coating them with a solid formulation. The compositioncan also be applied to the planting site when the propagation materialis being planted, for example to the seed furrow during sowing. Theinvention relates also to such methods of treating plant propagationmaterial and to the plant propagation material so treated.

PREPARATION EXAMPLES Example A1.14″-Desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1

11.9 g of 4″-desoxy-4″-(N-hydroxy-imino)-avermectin B1 are dissolved in36 ml of tetrahydrofuran. 4.5 ml pivalic acid and 0.5 ml of water areadded, followed by 2.1 g sodium cyanoborohydride. The mixture is stirredat room temperature for 14 hours at room temperature. Then 30 mlsaturated aqueous sodium bicarbonate are added and the mixture isextracted with ethyl acetate. The phases are then separated; the organicphase is dried over sodium sulfate and the solvents are distilled off.The residue is purified by chromatography on silica gel withhexane/ethyl acetate, yielding4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1.

Example A1.2 4″-Desoxy-4″-(R)—(N-methoxy-amino)-avermectin B1

8 g of 4″-desoxy-4″-(N-methoxy-imino)-avermectin B1 are dissolved in 20ml of tetrahydrofuran. 1.9 ml pivalic acid and 0.4 ml of water areadded, followed by 0.73 g sodium cyanoborohydride. The mixture isstirred at room temperature for 14 hours at room temperature. Then 20 mlsaturated aqueous sodium bicarbonate are added and the mixture isextracted with ethyl acetate. The phases are then separated; the organicphase is dried over sodium sulfate and the solvents are distilled off.The residue is purified by chromatography on silica gel withhexane/ethyl acetate, yielding4″-desoxy-4″-(R)—(N-methoxy-amino)-avermectin B1.

Example A1.3 4″-Desoxy-4″-(R)—(N-methoxycarbonyloxy-amino)-avermectin B1

4.4 g 4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1 (Example A1.1)are dissolved in a mixture of 30 ml ethyl acetate and 30 ml saturatedaqueous sodium bicarbonate. 0.47 g methyl chloroformate are added andthe mixture is vigorously stirred for 14 hours at room temperature. Thephases are then separated; the organic phase is dried over sodiumsulfate and the solvents are distilled off. The residue is purified bychromatography on silica gel with hexane/ethyl acetate, yielding4′-desoxy-4′-(R)—(N-methoxycarbonyloxy-amino)-avermectin B1 (ExampleA1.3) and4″-desoxy-4″-(R)—(N-hydroxy-N-methoxycarbonyl-amino)-avermectin B1(Example A2.7).

Example A1.44″-Desoxy-4″-(R)—(N-phenylaminocarbonyloxy-amino)-avermectin B1

4.4 g 4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1 (Example A1.1)are dissolved in 30 ml ethyl acetate. 0.72 g phenylisocyanate are addedand the mixture is stirred for 3 hours at room temperature. Then thesolvent is distilled off, and the residue is purified by chromatographyon silica gel with hexane/ethyl acetate, yielding4″-desoxy-4″-(R)—(N-phenyl-aminocarbonyloxy-amino)-avermectin B1(Example A1.4) and4″-desoxy-4″-(R)—(N-hydroxy-N-phenylaminocarbonyl-amino)-avermectin B1(Example A2.8).

Example A2.1 4″-Desoxy-4″-(R)—(N-hydroxy-N-methyl-amino)-avermectin B1

3.6 g 4″-desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1(Example A7.1) are dissolved in 40 ml tetrahydrofuran. 0.28 g sodiumcyanoborohydride are added, and the mixture is stirred for 4 hours atroom temperature. Then the mixture is extracted with aqueous sodiumbicarbonate (1 mol/l) and ethyl acetate. The phases are separated; theorganic phase is dried over sodium sulfate and the solvents aredistilled off. The residue is purified by chromatography on silica gelwith hexane/ethyl acetate, yielding4″-desoxy-4″-(R)—(N-hydroxy-N-methyl-amino)-avermectin B1.

Example A2.2 4″-Desoxy-4″-(R)—(N-hydroxy-N-ethyl-amino)-avermectin B1

4.5 g 4″-desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1(Example A7.1) are dissolved in 80 ml tetrahydrofuran. 6.7 mlmethylmagnesium bromide (3 mol/l solution in diethylether) are added,and the mixture is stirred for 1 hour at room temperature. Then themixture is extracted with saturated aqueous ammonium chloride and ethylacetate. The phases are separated; the organic phase is dried oversodium sulfate and the solvents are distilled off. The residue ispurified by chromatography on silica gel with hexane/ethyl acetate,yielding 4″-desoxy-4″-(R)—(N-hydroxy-N-ethyl-amino)-avermectin B1.

Example A2.3 4″-Desoxy-4″-(R)—(N-hydroxy-N-isopropyl-amino)-avermectinB1

4.3 g 4″-desoxy-4″-(R)—(N-ethylidene-amino)-avermectin-N-oxide B1(Example A7.2) are dissolved in 50 ml tetrahydrofuran. 5 mlmethylmagnesium bromide (3 mol/l solution in diethylether) are added,and the mixture is stirred for 1 hour at room temperature. Then themixture is extracted with saturated aqueous ammonium chloride and ethylacetate. The phases are separated; the organic phase is dried oversodium sulfate and the solvents are distilled off. The residue ispurified by chromatography on silica gel with hexane/ethyl acetate,yielding 4″-desoxy-4″-(R)—(N-hydroxy-N-isopropyl-amino)-avermectin B1.

Example A2.4 4″-Desoxy-4″-(R)—(N-hydroxy-N-benzyl-amino)-avermectin B1

2.7 g of 4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1 (Example A1.1)are dissolved in a mixture of 30 ml ethyl acetate and 30 ml saturatedaqueous sodium bicarbonate. Then 5.2 g benzyl bromide are added, and themixture is stirred for 48 hours at 60° C. After cooling to roomtemperature, the phases are separated; the organic phase is dried oversodium sulfate and the solvents are distilled off. The residue ispurified by chromatography on silica gel with hexane/ethyl acetate,yielding 4″-desoxy-4″-(R)—(N-hydroxy-N-benzyl-amino)-avermectin B1.

Example A2.54″-Desoxy-4″-(R)-[N-hydroxy-N-(2-ethoxycarbonyl-ethyl)-amino]-avermectinB1

4.5 g of 4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1 (Example A1.1)are dissolved in 10 ml of ethyl acrylate. The mixture is stirred at roomtemperature for 18 hours, then the solvent is distilled off. The residueis purified by chromatography on silica gel with hexane/ethyl acetate,yielding4″-desoxy-4″-(R)-[N-hydroxy-N-(2-ethoxycarbonyl-ethyl)-amino]-avermectinB1.

Example A2.64″-Desoxy-4″-(R)-[N-hydroxy-N-(4-hydroxy-4-methyl-pent-2-yn-1-yl)-amino]-avermectinB1

Under an atmosphere of nitrogen, 0.46 g 2-methyl-3-butyne-2-ol and 1.4 gN-ethyl-N,N-diisopropylamine are dissolved in 100 ml dichloromethane.Then 1.8 g zinc trifluoro-methanesulfonate are added, and the mixture isstirred for 3 hours at room temperature. Then a solution of 4.5 g4″-desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1 (ExampleA7.1) in 100 ml toluene are added. Subsequently, most of thedichloromethane is distilled off, and the remaining solution is stirredat 70° C. for 14 hours. Then the mixture is cooled to room temperature,extracted with saturated aqueous sodium bicarbonate and ethyl acetate,the phases are separated, the organic phase is dried over sodium sulfateand the solvent is distilled off. The residue is purified bychromatography on silica gel with hexane/ethyl acetate, yielding4″-Desoxy-4″-(R)-[N-hydroxy-N-(4-hydroxy-4-methyl-pent-2-yn-1-yl)-amino]-avermectinB1.

Example A2.74″-desoxy-4″-(R)—(N-hydroxy-N-methoxycarbonyl-amino)-avermectin B1

The compound is obtained by the same procedure as described in ExampleA1.3.

Example A2.84″-desoxy-4″-(R)—(N-hydroxy-N-phenylaminocarbonyl-amino)-avermectin B1

The compound is obtained by the same procedure as described in ExampleA1.4.

Example A3.14″-Desoxy-4″-(R)-(5-hydroxymethyl-isoxazolidin-2-yl)-avermectin B1

4.5 g 4″-desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1(Example A7.1) and 4.4 ml prop-2-en-1-ol are dissolved in 150 ml oftoluene. The mixture is stirred for 14 hours at 80° C. Then the solventis distilled off. The residue is purified by chromatography on silicagel with hexane/ethyl acetate, yielding4″-desoxy-4″-(R)-(5-hydroxymethyl-isoxazolidin-2-yl)-avermectin B1.

Example A3.24″-Desoxy-4″-(R)-(4,5-bis-ethoxycarbonyl-3H-isoxazol-2-yl)-avermectin B1

4.5 g 4″-desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1(Example A7.1) is dissolved in 60 ml of tetrahydrofuran. The mixture iscooled to 0° C., then 0.9 ml but-2-yne-dioic acid diethyl ester areadded, and the mixture is stirred at 0° C. for 3 hours. Then the solventis distilled off and the residue is purified by chromatography on silicagel with hexane/ethyl acetate, yielding4″-desoxy-4″-(R)-(4,5-bis-ethoxycarbonyl-3H-isoxazol-2-yl)-avermectinB1.

Example A4.1 4″-Desoxy-4″-(S)—(N-hydroxy-amino)-avermectin B1

7.7 g 4″-desoxy-4″-(S)—(N-cyanomethylene-amino)-avermectin-N-oxide B1(Example A8.1) are dissolved in 50 ml methanol, 2.8 g hydroxylaminehydrochloride and 3.6 g sodium bicarbonate are added, and the mixture isstirred at 60° C. for 3 hours. After cooling to room temperature, thesolvent is distilled off, and the residue is extracted with aqueoussodium bicarbonate (1 mol/l) and ethyl acetate. Then the phases areseparated; the organic phase is dried over sodium sulfate and thesolvent is distilled off. The residue is purified by chromatography onsilica gel with hexane/ethyl acetate, yielding4″-desoxy-4″-(S)—(N-hydroxy-amino)-avermectin B1.

Example A5.1 4″-Desoxy-4″-(R)—(N-hydroxy-amino)-22,23-dihydro-avermectinB1

4.8 g of 4″-desoxy-4″-(N-hydroxy-imino)-22,23-dihydro-avermectin B1 aredissolved in 15 ml of tetrahydrofuran. 1.8 ml pivalic acid and 0.2 ml ofwater are added, followed by 0.9 g sodium cyanoborohydride. The mixtureis stirred at room temperature for 14 hours at room temperature. Then 15ml saturated aqueous sodium bicarbonate are added and the mixture isextracted with ethyl acetate. The phases are then separated; the organicphase is dried over sodium sulfate and the solvents are distilled off.The residue is purified by chromatography on silica gel withhexane/ethyl acetate, yielding4″-desoxy-4″-(R)—(N-hydroxy-amino)-22,23-dihydro-avermectin B1.

Example A6.1 4′-Desoxy-4′-(R)—(N-hydroxy-amino)-avermectinmonosaccharide B1

10 g of 4′-desoxy-4′-(N-hydroxy-imino)-avermectin monosaccharide B1 aredissolved in 40 ml of tetrahydrofuran. 4.5 ml pivalic acid and 0.5 ml ofwater are added, followed by 2.6 g sodium cyanoborohydride. The mixtureis stirred at room temperature for 14 hours at room temperature. Then 40ml saturated aqueous sodium bicarbonate are added and the mixture isextracted with ethyl acetate. The phases are then separated; the organicphase is dried over sodium sulfate and the solvents are distilled off.The residue is purified by chromatography on silica gel withhexane/ethyl acetate, yielding4′-desoxy-4′-(R)—(N-hydroxy-amino)-avermectin monosaccharide B1.

Example A7.1 4″-Desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1

8.9 g 4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1 (Example A1.1)are dissolved in 50 ml ethyl acetate, 70 ml aqueous formaldehyde areadded, and the mixture is stirred vigorously for 3 hours at roomtemperature. The phases are then separated; the organic phase is driedover sodium sulfate and the solvents are distilled off. The residue ispurified by chromatography on silica gel with hexane/ethyl acetate,yielding 4″-desoxy-4″-(R)—(N-methylene-amino)-avermectin-N-oxide B1.

Example A7.2 4″-Desoxy-4″-(R)—(N-ethylidene-amino)-avermectin-N-oxide B1

8.9 g 4″-desoxy-4″-(R)—(N-hydroxy-amino)-avermectin B1 (Example A1.1)are dissolved in 50 ml acetaldehyde, and the mixture is stirred for 30minutes at room temperature. Then the solvent is distilled off. Theresidue is purified by chromatography on silica gel with hexane/ethylacetate, yielding4″-desoxy-4″-(R)—(N-ethylidene-amino)-avermectin-N-oxide B1.

Example A8.14″-Desoxy-4″-(S)—(N-cyanomethylene-amino)-avermectin-N-oxide B1

3 g 4″-desoxy-4″-(S)—(N-cyanomethyl-amino)-avermectin B1 are dissolvedin 20 ml dichloromethane, 1.6 g 3-chloroperbenzoic acid are added andthe mixture is stirred for 30 minutes at room temperature. Then 20 mlaqueous sodium bicarbonate (1 mol/l) are added, and after extraction thephases are separated; the organic phase is dried over sodium sulfate andthe solvent is distilled off. The residue is purified by chromatographyon silica gel with hexane/ethyl acetate, yielding4″-desoxy-4″-(S)—(N-cyanomethylene-amino)-avermectin-N-oxide B1.

Similarly to the preparation examples above it is also possible toprepare the compounds listed in Tables A1 to A8 and Tables 1 to 48. Inthe Tables, the symbol

denotes the bond through which the radical in question is attached tothe N-, O- or C-atom of the skeleton.

Since in most cases the compounds are present as mixtures of theavermectin derivatives B1a and B1b, characterization by customaryphysical data such as melting point or refractive index makes littlesense. For this reason, the compounds are characterized by the retentiontimes which are determined in an analysis by HPLC (high performanceliquid chromatography). Here, the term B1a refers to the main componentin which R₁ is sec-butyl, with a content of usually more than 80%. B1bdenotes the minor component in which R₁ is isopropyl. Where tworetention times are given both for the B1a and for the B1b derivative orboth, the compounds are mixtures of diastereomers which can be separatedchromatographically. In the case of compounds where a retention time isgiven only in column B1a or only in column B1b, the pure B1a or B1bcomponent, respectively, can be obtained during work-up. The correctstructures of the B1a and B1b components are assigned by massspectrometry.

The following method is used for HPLC analysis:

HPLC gradient conditions Solvent A: 0.01% of trifluoroacetic acid in H₂OSolvent B: 0.01% of trifluoroacetic acid in CH₃CN Time [min] A [%] B [%]Flow rate [μl/min] 0 80 20 500 0.1 50 50 500 10 5 95 500 15 0 100 500 170 100 500 17.1 80 20 500 22 80 20 500 Type of column YMC-Pack ODS-AQColumn length 125 mm Internal diameter of column: 2 mm Temperature 40°C.

The YMC-Pack ODS-AQ column used for the chromatography of the compoundsis manufactured by YMC, Alte Raesfelderstrasse 6, 46514 Schermbeck,Germany.

TABLE A1 Compounds of the formula (I) in which R₁ is sec-butyl orisopropyl

Retention time (min) No. R₃ B1a B1b A1.1 H 5.10 4.76 A1.2 methyl 9.168.44 A1.3

9.54 8.86 A1.4

11.18 A1.5 ethyl 9.50 8.85 A1.6 CH₂═CH—CH₂— 10.41 9.73 A1.7

9.18 8.58 A1.8 CH3OCH2CH2OCH2— 5.39 A1.9

8.16 7.47

TABLE A2 Compounds of the formula (I) in which R₁ is sec-butyl orisopropyl

Retention time (min) No. R₃ B1a B1b A2.1 methyl 6.59 6.19 A2.2 ethyl5.65 5.18 A2.3 iso-propyl 5.66 5.01 A2.4

9.55 9.12 A2.5

10.14 9.50 A2.6

7.10 6.52 A2.7

7.90 7.28 A2.8

9.50 A2.9 CH₂═CH—CH₂— 6.38 5.89 A2.10 n-propyl 6.03 5.55 A2.11 n-butyl6.44 5.92 A2.12

9.35 8.73 A2.13

9.30 8.75 A2.14

9.09 A2.15 CH≡C—CH₂— 8.66 8.01 A2.16 n-pentyl 7.02 6.45 A2.17

10.35 9.55 A2.18

6.88

TABLE A3 Compounds of the formula (I) in which R₁ is sec-butyl B1a) orisopropyl

No.

Retention time (min) B1a     B1b A3.1

5.53/5.42 5.12/5.07 A3.2

11.07 A3.3

9.47/8.87 A3.4

9.40/9.10 A3.5

8.48/8.27

TABLE A4 Compounds of the formula (I) in which and R₁ is sec-butylorisopropyl

Retention time (min) No. R₂ R₃ B1a B1b A4.1 H H 5.23 A4.2 HCH₃OCH₂CH₂OCH₂— 5.68

TABLE A5 Compounds of the formula (I) in which A is A1, n is 1, X—Y is—CH₂—CH₂— and R₁ is sec-butyl (B1a) or isopropyl (B1b).

Retention time (min) No. R₂ R₃ B1a B1b A5.1 H H 6.93 6.45 A5.2

H 12.12 11.47

TABLE A6 Compounds of the formula (I) in which R₁ is sec-butyl orisopropyl

Retention time (min) No. R₂ R₃ B1a B1b A6.1 H H 4.96 A6.2 H H 6.93 6.45A6.3

H 12.12 11.47

TABLE A7 Compounds of the formula (I) in which R₁ is sec-butyl B1a) orisopropyl

Retention time (min) No. R_(Z) R_(E) B1a B1b A7.1 H H A7.2 methyl H 7.316.62 A7.3 ethyl H 8.16 A7.4 iso-propyl H 8.70 8.05 A7.5 phenyl H 11.5810.78 A7.6 CN H 9.45 9.05 A7.7 n-butyl H 9.12 8.37 A7.8

H 10.47 9.81

TABLE A8 Compounds of the formula (I) in which R₁ is sec-butyl orisopropyl

Retention time (min) No. R_(Z) R_(E) B1a B1b A8.1 CN H 10.01

TABLE B Compounds of the formula (I) and (II) wherein U is —N(R₂)OR₃ andR₂ and R₃ have the following meanings: No. R₂ R₃ B1.1 methyl H B1.2ethyl H B1.3 n-propyl H B1.4 iso-propyl H B1.5 n-butyl H B1.6 s-butyl HB1.7 iso-butyl H B1.8 t-butyl H B1.9 CH₂═CH—CH₂— H B1.10 CH₃—CH═CH—CH₂—H B1.11 HO—CH₂—CH₂— H B1.12 phenyl H B1.13 benzyl H B1.14

H B1.15

H B1.16

H B1.17

H B1.18

H B1.19

H B1.20

H B1.21

H B1.22

H B1.23

H B1.24

H B1.25

H B1.26

H B1.27 benzoyl H B1.28

H B1.29

H B1.30

H B1.31

H B1.32

H B1.33

H B1.34 —CN H B1.35 H methyl B1.36 ethyl methyl B1.37 CH₂═CH—CH₂— methylB1.38 phenyl methyl B1.39 Benzyl methyl B1.40

methyl B1.41

methyl B1.42

methyl B1.43

methyl B1.44

methyl B1.45

methyl B1.46 Benzoyl Methyl B1.47

Methyl B1.48

Methyl B1.49

methyl B1.50 H methyl B1.51 H Ethyl B1.52 H n-propyl B1.53 H iso-propylB1.54 H n-butyl B1.55 H s-butyl B1.56 H iso-butyl B1.57 H t-butyl B1.58H CH₂═CH—CH₂— B1.59 H CH₃—CH═CH—CH₂— B1.60 H HO—CH₂—CH₂— B1.61 H phenylB1.62 H benzyl B1.63 H

B1.64 H

B1.65 H

B1.66 H

B1.67 H

B1.68 H

B1.69 H

B1.70 H

B1.71 H

B1.72 H

B1.73 H

B1.74 H

B1.75 H

B1.76 H

B1.77 H

B1.78 H

B1.79 H

B1.80 H

B1.81 H

B1.82 H

B1.83 H —CN B1.84 methyl H B1.85 methyl Ethyl B1.86 methyl CH₂═CH—CH₂—B1.87 methyl phenyl B1.88 methyl Benzyl B1.89 methyl

B1.90 methyl

B1.91 methyl

B1.92 methyl

B1.93 methyl

B1.94 methyl

B1.95 methyl benzoyl B1.96 methyl

B1.97 methyl

B1.98 methyl

B1.99 methyl —CN B1.100 methyl methyl B1.101 ethyl Ethyl B1.102 ethylCH₂═CH—CH₂— B1.103 ethyl

B1.104 ethyl

B1.105 ethyl

B1.106 ethyl

B1.107 ethyl —CN B1.108 CH₂═CH—CH₂— Ethyl B1.109

Ethyl B1.110

Ethyl B1.111

Ethyl B1.112

Ethyl B1.113 —CN Ethyl B1.114 CH₂═CH—CH₂— CH₂═CH—CH₂— B1.115 CH₂═CH—CH₂—

B1.116 CH₂═CH—CH₂—

B1.117 CH₂═CH—CH₂—

B1.118 CH₂═CH—CH₂—

B1.119 CH₂═CH—CH₂— —CN B1.120

CH₂═CH—CH₂— B1.121

CH₂═CH—CH₂— B1.122

CH₂═CH—CH₂— B1.123

CH₂═CH—CH₂— B1.124 —CN CH₂═CH—CH₂— B1.125 —CH₂—CH₂—CH₂— B1.126—CH₂—CH₂—CH₂— B1.127

B1.128

B1.129

B1.130

B1.131

B1.132

B1.133

B1.134

B1.135

B1.136

B1.137

B1.138

B1.139

B1.140

B1.141

B1.142

B1.143

B1.144

B1.145

B1.146

B1.147

B1.148

B1.149

B1.150

B1.151

B1.152

B1.153

B1.154

B1.155

B1.156

B1.157

B1.158

B1.159

B1.160

TABLE C Compounds of the formula (I) wherein U is —N⁺(O⁻)═C(R_(E))R_(Z))and R_(E) and R_(Z) have the following meanings: R_(E) R_(Z) C1.1 H HC1.2 methyl H C1.3 ethyl H C1.4 n-propyl H C1.5 iso-propyl H C1.6n-butyl H C1.7 s-butyl H C1.8 iso-butyl H C1.9 t-butyl H C1.10CH₂═CH—CH₂— H C1.11 CH₃—CH═CH—CH₂— H C1.12 phenyl H C1.13

H C1.14

H C1.15

H C1.16 4-F-phenyl H C1.17 4-Cl-phenyl H C1.18

H C1.19 4-Br-phenyl H C1.20

H C1.21

H C1.22

H C1.23 CN H C1.24 CF₃— H C1.25 CCl₃— H C1.26 CF₃—CH₂— H C1.27 CF₃—CF₂—H C1.28 CO₂—CH₃ H C1.29 CO₂—C₂H₅ H C1.30 HO—CH₂— H C1.31 CO—NH₂ H C1.32CO—NH—CH₃ H C1.33 CO—N(CH₃)₂ H C1.34 CH3—O—CH₂— H C1.35 C₂H₅—O—CH₂— HC1.36 H methyl C1.37 methyl methyl C1.38 ethyl methyl C1.39 n-propylmethyl C1.40 iso-propyl methyl C1.41 n-butyl methyl C1.42 s-butyl methylC1.43 iso-butyl methyl C1.44 t-butyl methyl C1.45 CH₂═CH—CH₂— methylC1.46 CH₃—CH═CH—CH₂— methyl C1.47 phenyl methyl C1.48

methyl C1.49

methyl C1.50

methyl C1.51 4-F-phenyl methyl C1.52 4-Cl-phenyl methyl C1.53

methyl C1.54 4-Br-phenyl methyl C1.55

methyl C1.56

methyl C1.57

methyl C1.58 CN methyl C1.59 CF₃— methyl C1.60 CCl₃— methyl C1.61CF₃—CH₂— methyl C1.62 CF₃—CF₂— methyl C1.63 CO₂—CH₃ methyl C1.64CO₂—C₂H₅ methyl C1.65 HO—CH₂— methyl C1.66 CO—NH₂ methyl C1.67 CO—NH—CH₃methyl C1.68 CO—N(CH₃)₂ methyl C1.69 CH3—O—CH₂— methyl C1.70 C₂H₅—O—CH₂—methyl C1.71 CN CN C1.72 CF₃— CF₃— C1.73 CCl₃— CCl₃— C1.74 CN CN C1.75CO₂—CH₃ CO₂—CH₃ C1.76 CO₂—C₂H₅ CO₂—C₂H₅ C1.77 CO₂—C₂H₅ CN C1.78 CNCO₂—C₂H₅ C1.79 Phenyl CF₃— C1.80 Phenyl CN C1.81 —CH₂—CH₂—CH₂— C1.82—CH₂—CH₂—CH₂—CH₂— C1.83

C1.84

C1.85

C1.86

C1.87

C1.88

C1.89

C1.90

C1.91

C1.92

C1.93

C1.94

C1.95

C1.96

C1.97

C1.98

C1.99

C1.100

Table Z1: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 1, X—Y is —CH═CH—, R₁is sec-butyl or isopropyl and R₃ for each compound corresponds to a lineB1.1 to B1.160 of Table B.

Table Z2: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 1, X—Y is —CH═CH—, R₁is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z3: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 1, X—Y is —CH₂—CH₂—,R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z4: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 1, X—Y is —CH₂—CH₂—,R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z5: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 0, X—Y is —CH═CH—, R₁is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z6: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 0, X—Y is —CH═CH—, R₁is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z7: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 0, X—Y is —CH₂—CH₂—,R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z8: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 0, X—Y is —CH₂—CH₂—,R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z9: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 1, X—Y is —CH═CH—, R₁cyclohexyl and R₃ for each compound corresponds to a line B1.1 to B1.160of Table B.

Table Z10: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 1, X—Y is —CH═CH—, R₁cyclohexyl and R₃ for each compound corresponds to a line B1.1 to B1.160of Table B.

Table Z11: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 1, X—Y is —CH₂—CH₂—,R₁ is cyclohexyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z12: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 1, X—Y is —CH₂—CH₂—,R₁ is cyclohexyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z13: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 0, X—Y is —CH═CH—, R₁is cyclohexyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z14: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 0, X—Y is —CH═CH—, R₁is cyclohexyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z15: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 0, X—Y is —CH₂—CH₂—,R₁ is cyclohexyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z16: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 0, X—Y is —CH₂—CH₂—,R₁ is cyclohexyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z17: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 1, X—Y is —CH═CH—, R₁is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z18: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 1, X—Y is CH═CH—, R₁is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z19: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 1, X—Y is —CH₂—CH₂—,R₁ is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1to B1.160 of Table B.

Table Z20: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 1, X—Y is —CH₂—CH₂—,R₁ is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1to B1.160 of Table B.

Table Z21: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 0, X—Y is CH═CH—, R₁is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z22: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 0, X—Y is —CH═CH—, R₁is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1 toB1.160 of Table B.

Table Z23: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is H, n is 0, X—Y is —CH₂—CH₂—,R₁ is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1to B1.160 of Table B.

Table Z24: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is H, n is 0, X—Y is —CH₂—CH₂—,R₁ is 1-methyl-butyl and R₃ for each compound corresponds to a line B1.1to B1.160 of Table B.

Table Z25: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH═CH—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for eachcompound corresponds to a line B1.1 to B1.160 of Table B.

Table Z26: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH═CH—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for eachcompound corresponds to a line B1.1 to B1.160 of Table B.

Table Z27: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH₂—CH₂—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ foreach compound corresponds to a line B1.1 to B1.160 of Table B.

Table Z28: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH₂—CH₂—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ foreach compound corresponds to a line B1.1 to B1.160 of Table B.

Table Z29: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH═CH—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for eachcompound corresponds to a line B1.1 to B1.160 of Table B.

Table Z30: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH═CH—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ for eachcompound corresponds to a line B1.1 to B1.160 of Table B.

Table Z31: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH₂—CH₂—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ foreach compound corresponds to a line B1.1 to B1.160 of Table B.

Table Z32: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH₂—CH₂—, R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₃ foreach compound corresponds to a line B1.1 to B1.160 of Table B.

Table Z33: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH═CH—, R₁ cyclohexyl and R₃ for each compound corresponds to aline B1.1 to B1.160 of Table B.

Table Z34: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH═CH—, R₁ cyclohexyl and R₃ for each compound corresponds to aline B1.1 to B1.160 of Table B.

Table Z35: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH₂═CH₂—, R₁ is cyclohexyl and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table Z36: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH₂—CH₂—, R₁ is cyclohexyl and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table Z37: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH═CH—, R₁ is cyclohexyl and R₃ for each compound corresponds toa line B1.1 to B1.160 of Table B.

Table Z38: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH═CH—, R₁ is cyclohexyl and R₃ for each compound corresponds toa line B1.1 to B1.160 of Table B.

Table Z39: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH₂—CH₂—, R₁ is cyclohexyl and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table Z40: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH₂—CH₂—, R₁ is cyclohexyl and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table Z41: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH═CH—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z42: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH═CH—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z43: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH₂—CH₂—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z44: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 1,X—Y is —CH₂—CH₂—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z45: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH═CH—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z46: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH═CH—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z47: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is E, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH₂—CH₂—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table Z48: A compound of the formula (II) in which the configuration ofthe C═N bond at the ε-position is Z, G is t-butyl-dimethylsilyl, n is 0,X—Y is —CH₂—CH₂—, R₁ is 1-methyl-butyl and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of

Table Z49: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z50: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z51: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z52: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z53: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 0, X—Y is —CH═CH—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z54: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z55: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z56: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is sec-butyl(B1a) or isopropyl (B1b) and the combination of R_(Z) and R_(E) for eachcompound corresponds to a line C1.1 to C1.100 of Table C.

Table Z57: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ cyclohexyl andthe combination of R_(Z) and R_(E) for each compound corresponds to aline C1.1 to C1.100 of Table C.

Table Z58: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ cyclohexyl andthe combination of R_(Z) and R_(E) for each compound corresponds to aline C1.1 to C1.100 of Table C.

Table Z59: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z60: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z61: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 0, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R_(Z) and R_(E) for each compound corresponds toa line C1.1 to C1.100 of Table C.

Table Z62: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R_(Z) and R_(E) for each compound corresponds toa line C1.1 to C1.100 of Table C.

Table Z63: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z64: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z65: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z66: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z67: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z68: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z69: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 0, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z70: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z71: A compound of the formula (III) in which the configuration ofthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table Z72: A compound of the formula (III) in which the configuration ofthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 1: A Compound of the formula (Ib) wherein the configuration at theε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 2: A Compound of the formula (Ib) wherein the configuration at theε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 3: A Compound of the formula (Ib) wherein the configuration at theε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 4: A Compound of the formula (Ib) wherein the configuration at theε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 5: A Compound of the formula (Ib) wherein the configuration at theε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 6: A Compound of the formula (Ib) wherein the configuration at theε-position is (R) G is H, n is 0, X—Y is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 7: A Compound of the formula (Ib) wherein the configuration at theε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 8: A Compound of the formula (Ib) wherein the configuration at theε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compound correspondsto a line B1.1 to B1.160 of Table B.

Table 9: A Compound of the formula (Ia) wherein the configuration at theε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 10: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is sec-butylor isopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 11: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is sec-butylor isopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 12: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is sec-butylor isopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 13: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is sec-butylor isopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 14: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R) G is H, n is 0, X—Y is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 15: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is sec-butylor isopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 16: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is sec-butylor isopropyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 17: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R₂ and R₃ for each compound corresponds to a lineB1.1 to B1.160 of Table B.

Table 18: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R₂ and R₃ for each compound corresponds to a lineB1.1 to B1.160 of Table B.

Table 19: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 20: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 21: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R₂ and R₃ for each compound corresponds to a lineB1.1 to B1.160 of Table B.

Table 22: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 0, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R₂ and R₃ for each compound corresponds to a lineB1.1 to B1.160 of Table B.

Table 23: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 24: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 25: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R_(Z) and R_(E) for each compound corresponds toa line C1.1 to C1.100 of Table C.

Table 26: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R_(Z) and R_(E) for each compound corresponds toa line C1.1 to C1.100 of Table C.

Table 27: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 28: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 29: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R_(Z) and R_(E) for each compound corresponds toa line C1.1 to C1.100 of Table C.

Table 30: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R) G is H, n is 0, X—Y is —CH═CH—, R₁ is cyclohexyland the combination of R_(Z) and R_(E) for each compound corresponds toa line C1.1 to C1.100 of Table C.

Table 31: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 32: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ iscyclohexyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 33: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 34: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 35: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 36: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 37: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 38: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R) G is H, n is 0, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 39: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 40: A Compound of the formula (Ib) wherein the configuration atthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R₂ and R₃ for each compoundcorresponds to a line B1.1 to B1.160 of Table B.

Table 41: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 42: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 43: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 44: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 1, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 45: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 46: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R) G is H, n is 0, X—Y is —CH═CH—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 47: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (S), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Table 48: A Compound of the formula (Ia) wherein the configuration atthe ε-position is (R), G is H, n is 0, X—Y is —CH₂—CH₂—, R₁ is1-methyl-butyl and the combination of R_(Z) and R_(E) for each compoundcorresponds to a line C1.1 to C1.100 of Table C.

Formulation Examples for Use in Crop Protection (% is Percent by Weight)

Example F1: Emulsion concentrates a) b) c) Active compound 25% 40% 50%Calcium dodecylbenzenesulphonate  5%  8%  6% Castor oil polyethyleneglycol ether (36 mol of EO)  5% — — Tributylphenol polyethylene glycolether (30 mol of — 12%  4% EO) Cyclohexanone — 15% 20% Xylene mixture65% 25% 20% Mixing of finely ground active compound and additives givesan emulsion concentrate which, by dilution with water, affords emulsionsof the desired concentration.

Example F2: Solutions a) b) c) d) Active compound 80% 10%  5% 95%Ethylene glycol monomethyl ether — 20% — — Polyethylene glycol (MW 400)— 70% — — N-methylpyrrolid-2-one 20% — — — Epoxidized coconut oil — — 1%  5% Petroleum ether (boiling range: 160-190°) — — 94% — Mixing offinely ground active compound and additives gives a solution suitablefor use in the form of microdrops.

Example F3: Granules a) b) c) d) Active compound  5% 10%  8% 21% Kaolin94% — 79% 54% Finely divided silicic acid  1% — 13%  7% Attapulgite —90% — 18% The active compound is dissolved in dichloromethane, thesolution is sprayed onto the mixture of carriers and the solvent isevaporated under reduced pressure.

Example F4: Wettable powder a) b) c) Active compound 25% 50% 75% Sodiumlignosulphonate  5%  5% — Sodium lauryl sulphate  3% —  5% Sodiumdiisobutylnaphthalene sulphonate —  6% 10% Octylphenol polyethyleneglycol ether (7-8 mol of —  2% — EO) Finely divided silicic acid  5% 10%10% Kaolin 62% 27% — Active compound and additives are mixed and themixture is ground in a suitable mill. This gives wettable powders whichcan be diluted with water to give suspensions of the desiredconcentration.

Example F5: Emulsion concentrate Active compound 10% Octylphenolpolyethylene glycol ether (4-5 mol of EO)  3% Calciumdodecylbenzenesulphonate  3% Castor oil polyethylene glycol ether (36mol of EO)  4% Cyclohexanone 30% Xylene mixture 50% Mixing of finelyground active compound and additives gives an emulsion concentratewhich, by dilution with water, affords emulsions of the desiredconcentration.

Example F6: Extruder granules Active compound 10% Sodium lignosulphonate 2% Carboxymethylcellulose  1% Kaolin 87% Active compound and additivesare mixed, the mixture is ground, moistened with water, extruded andgranulated, and the granules are dried in a stream of air.

Example 7: Coated granules Active compound  3% Polyethylene glycol (MW200)  3% Kaolin 94% In a mixer, the finely ground active compound isapplied uniformly to the kaolin which has been moistened withpolyethylene glycol. This gives dust-free coated granules.

Example F8: Suspension Concentrate

Example F8: Suspension concentrate Active compound 40% Ethylene glycol10% Nonylphenol polyethylene glycol ether (15 mol of EO) 6% Sodiumlignosulphonate 10% Carboxymethylcellulose 1% Aqueous formaldehydesolution (37%) 0.2% Aqueous silicone oil emulsion (75%) 0.8% Water 32%Mixing of finely ground active compound and additives gives a suspensionconcentrate which, by dilution with water, affords suspensions of thedesired concentration.

Biological Examples Example B1 Activity Against Spodoptera littoralis

Young soya bean plants are sprayed with an aqueous emulsion spray liquorwhich comprises 12.5 ppm of active compound, and, after the spraycoating has dried on, populated with 10 caterpillars of the first stageof Spodoptera littoralis and introduced into a plastic container. 3 dayslater, the reduction in the population in percent and the reduction inthe feeding damage in percent (% activity) are determined by comparingthe number of dead caterpillars and the feeding damage between thetreated and the untreated plants.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

Example B2 Activity Against Spodoptera littoralis, Systemic

Maize seedlings are placed into the test solution which comprises 12.5ppm of active compound. After 6 days, the leaves are cut off, placedonto moist filter paper in a Petri dish and populated with 12 to 15Spodoptera littoralis larvae of the L₁ stage. 4 days later, thereduction of the population in percent (% activity) is determined bycomparing the number of dead caterpillars between the treated and theuntreated plants.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

Example B3 Activity Against Heliothis virescens

30-35 0- to 24-hour-old eggs of Heliothis virescens are placed ontofilter paper in a Petri dish on a layer of synthetic feed. 0.8 ml of thetest solution which comprises 12.5 ppm of active compound is thenpipetted onto the filter papers. Evaluation is carried out after 6 days.The reduction in the population in percent (% activity) is determined bycomparing the number of dead eggs and larvae on the treated and theuntreated filter papers.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

Example B4 Activity Against Plutella xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray liquorwhich comprises 12.5 ppm of the active compound. After the spray coatinghas dried on, the cabbage plants are populated with 10 caterpillars ofthe first stage of Plutella xylostella and introduced into a plasticcontainer. Evaluation is carried out after 3 days. The reduction in thepopulation in percent and the reduction in the feeding damage in percent(% activity) are determined by comparing the number of dead caterpillarsand the feeding damage on the treated and the untreated plants.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

Example B5 Activity Against Frankliniella occidentalis

In Petri dishes, discs of the leaves of beans are placed onto agar andsprayed with test solution which comprises 12.5 ppm of active compoundin a spraying chamber. The leaves are then populated with a mixedpopulation of Frankliniella occidentalis. Evaluation is carried outafter 10 days. The reduction in percent (% activity) is determined bycomparing the population on the treated leaves with that of theuntreated leaves.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

Example B6 Activity Against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray liquor whichcomprises 12.5 ppm of active compound and, after the spray coating hasdried on, populated with 10 larvae of the second stage of Diabroticabalteata and then introduced into a plastic container. After 6 days, thereduction in the population in percent (% activity) is determined bycomparing the dead larvae between the treated and the untreated plants.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

Example B7 Activity Against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychusurticae and, after 1 day, sprayed with an aqueous emulsion spray liquorwhich comprises 12.5 ppm of active compound, incubated at 25° C. for 6days and then evaluated. The reduction in the population in percent (%activity) is determined by comparing the number of dead eggs, larvae andadults on the treated and on the untreated plants.

In this test, the compounds of the Tables A1 to A8 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A8.1 aremore than 80% effective.

1. A compound of the formula (I)

U is —N(R₂)OR₃ or —N⁺(O⁻)═C(R_(E))(R_(Z)); n is 0 or 1; X—Y is —CH═CH—or —CH₂—CH₂—; R₁ is C₁-C₁₂alkyl, C₃-C₈cycloalkyl or C₂-C₁₂alkenyl; R₂and R₃ are, independently from each other, —Q, —C(O)—Z—Q or —CN; R_(Z)and R_(E) are, independently from each other, —Q, —C(O)—Z—Q or —CN; orR_(Z) and R_(E) together are a three- to seven membered alkylene oralkenylene bridge, which is unsubstituted or mono- to tri-substituted; Zis a bond, O or —NR₄—; R₄ is H, C₁-C₈alkyl, hydroxy-C₁-C₈alkyl,C₃-C₈cycloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, phenyl, benzyl —C(═O)R₅, or—CH₂—C(═O)—R₅; Q is H, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl,C₃-C₁₂-cycloalkyl, C₅-C₁₂-cycloalkenyl, aryl, or heterocyclyl, which areunsubstituted or mono- to pentasubstituted; wherein the alkyl-,alkenyl-, alkynyl-, alkylene-, alkenylene-, cycloalkyl-, cycloalkenyl-,aryl- and heterocyclyl-radicals of the substituents Q, R₂, R₃, R₄,R_(Z), R_(E) and Q are independently of each other selected from thegroup consisting of OH, ═O, SH, ═S, halogen, CN, —N3, SCN, NO₂,Si(C₁-C₈alkyl)₃, halo-C₁-C₂alkyl, C₁-C₂alkoxy-C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy,C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy,C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy, C₂-C₁₂alkenylthio,C₂-C₁₂haloalkenylthio, C₂-C₁₂alkenylsulfinyl, C₂-C₁₂haloalkenylsulfinyl,C₂-C₁₂alkenylsulfonyl, C₂-C₁₂haloalkenylsulfonyl, C₃-C₈cycloalkyl whichis unsubstituted or substituted by one to three methyl groups,norbornylenyl, C₃-C₈halocycloalkyl, C₁-C₁₂alkoxy, C₃-C₈cycloalkoxy,C₁-C₁₂alkylthio, C₃-C₈cycloalkylthio, C₁-C₁₂haloalkylthio,C₁-C₁₂alkyl-sulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₁₂haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₁-C₁₂alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₁₂haloalkylsulfonyl,C₃-C₈halocycloalkylsulfonyl, C₂-C₈alkenyl, C₂-C₈alkynyl, —N(R₈)₂ whereinthe two R₈ are independent of each other, —C(═O)R₅, —O—C(O)R₆,—NHC(O)R₅, —S—C(═S)R₆, —P(═O)(OC₁-C₆alkyl)₂, —S(═O)₂R₉; —NH—S(═O)₂R₉,OC(═O)—C₁-C₆alkyl-S(O)₂R₉, aryl, benzyl, heterocyclyl, aryloxy,benzyloxy, heterocyclyloxy, arylthio, benzylthio, heterocyclylthio;wherein the aryl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy,arylthio, benzylthio and heterocyclylthio radicals are eitherunsubstituted or, depending on the possibilities of substitution on thering, mono- to pentasubstituted by substituents selected from the groupconsisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl,Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy,C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl,C₃-C₁₂haloalkynyloxy, C₃-C₈cycloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl,dimethylamino-C₁-C₆alkoxy, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy,phenyl-C₁-C₆alkyl, methylene-dioxy, —C(═O)R₅, —O—C(═O)—R₆, —NH—C(═O)R₆,—N(R₈)₂, wherein the two R₈ are independent of each other,C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl andC₃-C₈halocycloalkylsulfonyl; R₅ is H, OH, SH, —N(R₈)₂ wherein the two R₈are independent of each other, C₁-C₂4alkyl, C₂-C₁₂alkenyl,C₁-C₈hydroxyalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy,C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₁₂alkylthio, C₂-C₈alkenyloxy,C₃-C₈alkynyloxy, Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy,C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy,C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy, NH—C₁-C₆alkyl-C(═O)R₇,—N(C₁-C₆alkyl)-C₁-C₆alkyl-C(═O)—R₇, —O—C₁-C₂alkyl-C(═O)R₇,—C₁-C₆alkyl-S(═O)₂R₉, aryl, benzyl, heterocyclyl, aryloxy, benzyloxy,heterocyclyloxy; or aryl, benzyl, heterocyclyl, aryloxy, benzyloxy orheterocyclyloxy, which are independently of one another, depending onthe substitution possibilities, mono- to trisubstituted in the ring byhalogen, nitro, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl orC₁-C₆haloalkoxy; R₆ is H, C₁-C₂₄alkyl, C₁-C₁₂haloalkyl,C₁-C₁₂hydroxyalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, C₁-C₆alkoxy-C₁-C₆alkyl,Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy,C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl,C₃-C₁₂haloalkynyloxy, (NR₈)₂, wherein the two R₈ are independent of eachother, —C₁-C₆alkyl-C(═O)R₈, —C₁-C₆alkyl-S(═O)₂R₉, aryl, benzyl,heterocyclyl; or aryl, benzyl or heterocyclyl which, depending on thepossibilities of substitution on the ring, are mono- to trisubstitutedby substituents selected from the group consisting of OH, halogen, CN,NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₁-C₁₂alkylthio, Si(C₁-C₈alkyl)₃, C₁-C₁₂alkoxy-C₁-C₁2alkoxy,C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy,C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy,C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy and C₁-C₁₂halo-alkylthio; R₇ isH, OH, C₁-C₂4alkyl that is optionally substituted with OH, or—S(O)₂—C₁-C₆alkyl; C₁-C₁₂alkenyl, C₂-C₁₂alkynyl, C₁-C₁₂alkoxy,C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy, C₂-C₈alkenyloxy, aryl,aryloxy, benzyloxy, heterocyclyl, heterocyclyloxy or —N(R₈)₂, whereinthe two R₈ are independent of each other; R₈ is H, C₁-C₆alkyl, which isoptionally substituted with one to five substituents selected from thegroup consisting of halogen, hydroxy, cyano C₁-C₆alkoxy, ═O,C₂-C₁₂alkenyl, C₂-C₁₂haloalkenyl, C₂-C₁₂haloalkynyl andC₃-C₁₂haloalkynyloxy; C₃-C₈-cycloalkyl, aryl, benzyl, heteroaryl; oraryl, benzyl or heteroaryl, which, depending on the possibilities ofsubstitution on the ring, are mono- to trisubstituted by substituentsselected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl,C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, Si(C₁-C₈alkyl)₃,C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₃-C₈cycloalkoxy,C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy, C₂-C₁₂haloalkenyl,C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl, C₃-C₁₂haloalkynyloxy,C₁-C₁₂alkylthio and C₁-C₁₂haloalkylthio; R₉ is H, C₁-C₆alkyl, which isoptionally substituted with one to five substituents selected from thegroup consisting of halogen, C₁-C₆alkoxy, OH, ═O, C₂-C₁₂alkenyl,C₂-C₁₂haloalkenyl, C₂-C₁₂haloalkynyl, C₂-C₁₂haloalkynyl and cyano; aryl,benzyl, heteroaryl; or aryl, benzyl or heteroaryl, which, depending onthe possibilities of substitution on the ring, are mono- totrisubstituted by substituents selected from the group consisting of OH,halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, Si(C₁-C₈alkyl)₃,C₁-C₁₂alkoxy, C₁-C₁₂alkoxy-C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₃-C₈cycloalkoxy, C₂-C₁₂alkenyloxy, C₂-C₁₂haloalkenyloxy,C₂-C₁₂haloalkenyl, C₃-C₁₂alkynyloxy, C₂-C₁₂haloalkynyl,C₃-C₁₂haloalkynyloxy, C₁-C₁₂alkylthio and C₁-C₁₂haloalkylthio; or, ifappropriate, an E/Z isomer, E/Z isomer mixture and/or tautomer thereof.2. A pesticide composition which contains at least one compound of theformula (I) as described in claim 1 as active compound and at least oneauxiliary.
 3. A method for controlling pests comprising applying acomposition as described in claim 2 to the pests or a habitat of thepests.
 4. A process for preparing a composition as described in claim 2comprising intimately mixing and/or grinding the active compound with atleast one auxiliary.
 5. A method for protecting plant propagationmaterial, comprising applying the composition as described in claim 2 tothe propagation material or a location where the propagation material isplanted.
 6. Plant propagation material comprising a composition asdescribed in claim 2.